Patent Grant
11065608
The present invention provides, inter alia, multidentate ligand having the structure:
Also provided are metal complexes generated by the ligands of the present invention, as well as methods of using such ligands and complexes.
Despite their paucity, terminal metal hydride compounds offer much potential, and are often invoked as intermediates in a variety of catalytic cycles, including hydrosilylation, hydroboration, hydroamination, and hydrogenation (Harder 2012; Sarish et al 2011; Rochat et al 2016; Hill et al 2016; Arrowsmith 2015; Crimmin et al 2013; Revunova et al 2015; Dunne et al 2011; Schnitzler et al 2016; Spielmann et al 2008; Buch et al 2006). Such transformations offer potential societal benefits, especially considering that, for example, industrial hydrosilylation reactions typically employ precious metal catalysts (Meister et al 2016).
Also, the efficient utilization of carbon dioxide as a renewable C1 source for the synthesis of value-added organic chemicals and fuels is not only of intrinsic value, but also offers potential for abating the increasing levels of carbon dioxide in the atmosphere (Aresta 2010; Liu et al 2015; Fraga et al 2015). However, CO2 is thermodynamically very stable and kinetically resistant to many transformations, which presents a major impediment to achieving this objective.
Accordingly, there is a need for the exploration of various terminal metal hydride compounds that can be used in catalytic systems for hydrosilylation, hydroboration, hydroamination and hydrogenation that employ non-precious metals, occur at room temperature, and may be modified to control the level of reduction. This invention is directed to meet these and other needs.
One embodiment of the present invention is a compound multidentate ligand having the structure of formula (I):
wherein:
Another embodiment of the present invention is a multidentate ligand having the following structure:
Another embodiment of the present invention is a method of preparing a metal complex. This method comprises coordinating a ligand disclosed herein to a metal center via a combination of up to three nitrogen donors and a carbon atom.
Another embodiment of the present invention is a metal complex prepared by a method disclosed herein. The metal complex has the structure of formula (II):
wherein:
Another embodiment of the present invention is a metal complex prepared by a method disclosed herein. The metal complex has the following structure:
Another embodiment of the present invention is a metal complex prepared by a method disclosed herein. The metal complex has the following structure:
Another embodiment of the present invention is a catalyst. The catalyst comprises at least one metal complex disclosed herein.
Another embodiment of the present invention is a method of catalyzing hydrosilylation of styrenes. This method comprises providing a catalyst disclosed herein to a hydrosilylation reaction of a styrene.
Another embodiment of the present invention is a method of catalyzing hydroboration of styrenes. This method comprises providing a catalyst disclosed herein to a hydroboration reaction of a styrene.
Another embodiment of the present invention is a method of catalyzing hydrosilylation of carbon dioxide. This method comprises providing a catalyst disclosed herein to a hydrosilylation reaction of carbon dioxide.
Another embodiment of the present invention is a method of preparing a formaldehyde equivalent from carbon dioxide. This method comprises contacting a reaction mixture comprising carbon dioxide and a silane with a compound prepared from a multidentate ligand disclosed herein, wherein the silane is R3SiH and R is selected from H, alkyl and aryl.
A further embodiment of the present invention is a method of reducing carbon monoxide. This method comprises contacting a reaction mixture comprising carbon monoxide with a compound prepared from a multidentate ligand disclosed herein.
Another embodiment of the present invention is a method of catalyzing hydrogenation of alkenes or alkynes. This method comprises providing a catalyst disclosed herein to a hydrogenation reaction of an alkene or an alkyne.
Another embodiment of the present invention is a method of catalyzing polymerization of alkenes. This method comprises providing a catalyst disclosed herein to a polymerization reaction of alkenes.
Another embodiment of the present invention is a method of catalyzing production of hydrogen-on-demand from alcohols or amines. This method comprises providing a catalyst disclosed herein to the reaction.
Another embodiment of the present invention is a method of catalyzing hydrosilylation of ketones or aldehydes. This method comprises providing a catalyst disclosed herein to a hydrosilylation reaction of a ketone or an aldehyde.
Another embodiment of the present invention is a method of catalyzing Tishchenko reaction. This method comprises providing a catalyst disclosed herein to the reaction.
Another embodiment of the present invention is a method of catalyzing hydrogenation of carbon dioxide. This method comprises providing a catalyst disclosed herein to a hydrogenation reaction of carbon dioxide.
Another embodiment of the present invention is a method of catalyzing hydrogenation of carbon monoxide. This method comprises providing a catalyst disclosed herein to a hydrogenation reaction of carbon monoxide.
The application file contains at least one photograph executed in color. Copies of this patent application with color photographs will be provided by the Office upon request and payment of the necessary fee.
In the present invention, multidentate ligands and metal complexes prepared from the same are provided. Certain of the metal complexes can be used in catalytic systems for hydrosilylation, hydroboration, hydroamination and hydrogenation. Accordingly, one aspect of the present invention is a multidentate ligand having the structure of formula (I):
wherein:
In some embodiments, the linker group Z comprises a silicon-containing group.
In some embodiments, the linker group Z is Si(R4)2; and wherein R4 is selected from the group consisting of H, halide, alkyl, aryl, aralkyl, heteroalkyl, heteroaryl, alkoxy, hydroxy, heteroalkoxy, amino, alkylamino, arylamino, cyano or a heterocyclic group.
Preferably, the multidentate ligand of this embodiment has the following structure:
Another embodiment of the present invention is method of preparing a metal complex. This method comprises coordinating a ligand disclosed herein to a metal center via a combination of up to three nitrogen donors and a carbon atom.
Preferably, the metal center comprises an atom selected from the main group metals, transition metals, or lanthanoids.
More preferably, the metal center comprises an atom selected from Li, Mg, Ca, Fe, Ni, Cu, Zn, Zr and Cd.
Another aspect of the present invention is a metal complex prepared by a method disclosed herein. The metal complex has the structure of formula (II):
wherein:
M is an atom selected from Li, Mg, Ca, Fe, Ni, Cu, Zn, Zr and Cd; and X is selected from no atom, H, Me, halogen, O2CH, S2CH, SH, N(H)Ph, CH(Me)Ph, O2CMe and S2CMe.
Preferably, the metal complex has a structure selected from the group consisting of:
More preferably, the metal complex has the following structure:
More preferably, the metal complex has the following structure:
Another aspect of the present invention is a catalyst. The catalyst comprises at least one metal complex disclosed herein.
Another aspect of the present invention is a method of catalyzing hydrosilylation of styrenes. This method comprises providing a catalyst disclosed herein to a hydrosilylation reaction of a styrene.
Another aspect of the present invention is a method of catalyzing hydroboration of styrenes. This method comprises providing a catalyst disclosed herein to a hydroboration reaction of a styrene.
Another aspect of the present invention is a method of catalyzing hydrosilylation of carbon dioxide. This method comprises providing a catalyst disclosed herein to a hydrosilylation reaction of carbon dioxide.
Still another aspect of the present invention is a method of preparing a formaldehyde equivalent from carbon dioxide. This method comprises contacting a reaction mixture comprising carbon dioxide and a silane with a compound prepared from a multidentate ligand disclosed herein, wherein the silane is R3SiH and R is selected from H, alkyl and aryl.
In some embodiments, the multidentate ligand has the structure:
In some embodiments, the compound comprises at least one metal complex disclosed herein.
A further aspect of the present invention is a method of reducing carbon monoxide. This method comprises contacting a reaction mixture comprising carbon monoxide with a compound prepared from a multidentate ligand disclosed herein.
In some embodiments, the multidentate ligand has the structure:
In some embodiments, the compound comprises at least one metal complex disclosed herein.
Another aspect of the present invention is a method of catalyzing hydrogenation of alkenes or alkynes. This method comprises providing a catalyst disclosed herein to a hydrogenation reaction of an alkene or an alkyne.
Another aspect of the present invention is a method of catalyzing polymerization of alkenes. This method comprises providing a catalyst disclosed herein to a polymerization reaction of alkenes.
Another aspect of the present invention is a method of catalyzing production of hydrogen-on-demand from alcohols or amines. This method comprises providing a catalyst disclosed herein to the reaction.
Another aspect of the present invention is a method of catalyzing hydrosilylation of ketones or aldehydes. This method comprises providing a catalyst disclosed herein to a hydrosilylation reaction of a ketone or an aldehyde.
Another aspect of the present invention is a method of catalyzing Tishchenko reaction. This method comprises providing a catalyst disclosed herein to the reaction.
Another aspect of the present invention is a method of catalyzing hydrogenation of carbon dioxide. This method comprises providing a catalyst disclosed herein to a hydrogenation reaction of carbon dioxide.
Another aspect of the present invention is a method of catalyzing hydrogenation of carbon monoxide. This method comprises providing a catalyst disclosed herein to a hydrogenation reaction of carbon monoxide.
In the foregoing embodiments, the following definitions apply.
The term “alkyl” refers to the radical of saturated aliphatic groups that does not have a ring structure, including straight-chain alkyl groups, and branched-chain alkyl groups. In certain embodiments, a straight chain or branched chain alkyl has 6 or fewer carbon atoms in its backbone (e.g., C1-C6 for straight chains, C3-C6 for branched chains). Such substituents include all those contemplated for aliphatic groups, as discussed below, except where stability is prohibitive.
The term “alkoxy”, as used herein, refers to an alkyl (carbon and hydrogen chain) group singularly bonded to oxygen; thus R—O. Related to alkoxy groups are aryloxy groups, which have an aryl group singular bonded to oxygen such as the phenoxy group (C6H5O—).
The term “alkene” or “olefin”, as used herein, refers to an unsaturated hydrocarbon that contains at least one carbon-carbon double bond.
The term “alkyne”, as used herein, refers to an unsaturated hydrocarbon containing at least one carbon-carbon triple bond.
The term “alkenyl”, as used herein, refers to an aliphatic group containing at least one double bond and unless otherwise indicated, is intended to include both “unsubstituted alkenyls” and “substituted alkenyls”, the latter of which refers to alkenyl moieties having substituents replacing a hydrogen on one or more carbons of the alkenyl group. Such substituents include all those contemplated for aliphatic groups, as discussed below, except where stability is prohibitive. For example, substitution of alkenyl groups by one or more alkyl, carbocyclyl, aryl, heterocyclyl, or heteroaryl groups is contemplated.
Moreover, unless otherwise indicated, the term “alkyl” as used throughout the specification, examples, and claims is intended to include both “unsubstituted alkyls” and “substituted alkyls”, the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. Indeed, unless otherwise indicated, all groups recited herein are intended to include both substituted and unsubstituted options.
The term “Cx-y” when used in conjunction with a chemical moiety, such as, alkyl and cycloalkyl, is meant to include groups that contain from x to y carbons in the chain. For example, the term “Cx-yalkyl” refers to substituted or unsubstituted saturated hydrocarbon groups, including straight-chain alkyl and branched-chain alkyl groups that contain from x to y carbons in the chain, including haloalkyl groups such as trifluoromethyl and 2,2,2-trifluoroethyl, etc.
The term “aryl” as used herein includes substituted or unsubstituted single-ring aromatic groups in which each atom of the ring is carbon. Preferably the ring is a 3 to 8-membered ring, more preferably a 6-membered ring. The term “aryl” also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is aromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls. Aryl groups include benzene, naphthalene, phenanthrene, phenol, aniline, and the like.
The term “alkyl-aryl” or “aralkyl” refers to an alkyl group substituted with at least one aryl group.
The term “alkyl-heteroaryl” refers to an alkyl group substituted with at least one heteroaryl group.
The term “alkenyl-aryl” refers to an alkenyl group substituted with at least one aryl group.
The term “alkenyl-heteroaryl” refers to an alkenyl group substituted with at least one heteroaryl group.
The term “amino,” as used herein, alone or in combination, refers to —NRR′, wherein R and R′ are independently chosen from hydrogen, alkyl (i.e., alkylamino), acyl, heteroalkyl, aryl (i.e., arylamino), cycloalkyl, heteroaryl, and heterocycloalkyl, any of which may themselves be optionally substituted. Additionally, R and R′ may combine to form heterocycloalkyl, either of which may be optionally substituted.
The term “amine”, as used herein, refers to a compound or a functional group that contains a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, where in one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group (these may respectively be called alkylamines and arylamines; amines in which both types of substituent are attached to one nitrogen atom may be called alkylarylamines).
The term “cyano,” as used herein, alone or in combination, refers to —CN.
The term “sulfonyl”, as used herein, alone or in combination, refers either to a functional group found primarily in sulfones or to a substituent obtained from a sulfonic acid by the removal of the hydroxyl group similarly to acyl groups. Sulfonyl groups can be written as having the general formula R—S(═O)2—R′, where there are two double bonds between the sulfur and oxygen.
The term “alcohol” means an organic compound in which the hydroxyl functional group (—OH) is bound to a saturated carbon atom.
The term “ketone” means an organic compound with the structure RC(═O)R′, wherein neither R and R′ can be hydrogen atoms.
The term “aldehyde” or “alkanal” means an organic compound containing a functional group with the structure —CHO, consisting of a carbonyl center (a carbon double-bonded to oxygen) with the carbon atom also bonded to hydrogen and to an R group, which is any generic alkyl or side chain. The group (without R) is the aldehyde group, also known as the formyl group.
The term “cycloalkyl,” or, alternatively, “carbocycle,” as used herein, alone or in combination, refers to a saturated or partially saturated monocyclic, bicyclic or tricyclic alkyl group wherein each cyclic moiety contains from 3 to 12 carbon atom ring members and which may optionally be a benzo fused ring system which is optionally substituted as defined herein. In certain embodiments, said cycloalkyl will comprise from 5 to 7 carbon atoms. Examples of such cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydronaphthyl, indanyl, octahydronaphthyl, 2,3-dihydro-1H-indenyl, adamantyl and the like. “Bicyclic” and “tricyclic” as used herein are intended to include both fused ring systems, such as decahydronaphthalene, octahydronaphthalene as well as the multicyclic (multicentered) saturated or partially unsaturated type. The latter type of isomer is exemplified in general by, bicyclo[1,1,1]pentane, camphor, adamantane, and bicyclo[3,2,1]octane.
The term “heteroatom” as used herein means an atom of any element other than carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen, and sulfur; more preferably, nitrogen and oxygen.
The term “heteroalkyl,” as used herein, alone or in combination, refers to a stable straight or branched chain, or cyclic hydrocarbon radical, or combinations thereof, fully saturated or containing from 1 to 3 degrees of unsaturation, consisting of the stated number of carbon atoms and from one to three heteroatoms chosen from 0, N, and S, and wherein the nitrogen and sulfur atoms may optionally be oxidized and the nitrogen heteroatom may optionally be quaternized. The heteroatom(s) O, N and S may be placed at any interior position of the heteroalkyl group.
The term “heteroaryl” includes substituted or unsubstituted aromatic single ring structures, preferably 3- to 8-membered rings, more preferably 5- to 7-membered rings, even more preferably 5- to 6-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms. The term “heteroaryl” also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heteroaromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls. Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine, and the like.
The terms “heterocycloalkyl” and, interchangeably, “heterocycle,” as used herein, alone or in combination, each refer to a saturated, partially unsaturated, or fully unsaturated monocyclic, bicyclic, or tricyclic heterocyclic group containing at least one heteroatom as a ring member, wherein each said heteroatom may be independently chosen from N, O, and S. Additionally, a heterocycloalkyl may contain one or two C(O), S(O), or S(O)2 groups as ring members. In certain embodiments, said heterocycloalkyl will comprise from 1 to 4 heteroatoms as ring members. In further embodiments, said heterocycloalkyl will comprise from 1 to 2 heteroatoms as ring members. In certain embodiments, said heterocycloalkyl will comprise from 3 to 8 ring members in each ring. In further embodiments, said heterocycloalkyl will comprise from 3 to 7 ring members in each ring. In yet further embodiments, said heterocycloalkyl will comprise from 5 to 6 ring members in each ring. “Heterocycloalkyl” and “heterocycle” are intended to include sulfones, sulfoxides, N-oxides of tertiary nitrogen ring members, and carbocyclic fused and benzo fused ring systems; additionally, both terms also include systems where a heterocycle ring is fused to an aryl group, as defined herein, or an additional heterocycle group. Examples of heterocycle groups include aziridinyl, azetidinyl, 1,3-benzodioxolyl, dihydroisoindolyl, dihydroisoquinolinyl, dihydrocinnolinyl, dihydrobenzodioxinyl, dihydro[1,3]oxazolo[4,5-b]pyridinyl, benzothiazolyl, dihydroindolyl, dihy-dropyridinyl, 1,3-dioxanyl, 1,4-dioxanyl, 1,3-dioxolanyl, isoindolinyl, morpholinyl, piperazinyl, pyrrolidinyl, tetrahydropyridinyl, piperidinyl, thiomorpholinyl, and the like. The heterocycle groups may be optionally substituted unless specifically prohibited.
The term “hydroxy,” as used herein, alone or in combination, refers to —OH.
The terms “halo” and “halogen” are used interchangeably herein and mean halogen and include chloro, fluoro, bromo, and iodo.
The term “halide”, as used herein, refers to a binary phase, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fluoride, chloride, bromide, or iodide compound. The alkali metals combine directly with halogens under appropriate conditions forming halides of the general formula, MX (X═F, Cl, Br or I).
The term “haloalkoxy,” as used herein, alone or in combination, refers to a haloalkyl group attached to the parent molecular moiety through an oxygen atom. Haloalkoxy includes perhaloalkoxy. The term “perhaloalkoxy” refers to an alkoxy group where all of the hydrogen atoms are replaced by halogen atoms. An example of perhaloalkoxy is perfluoromethoxy.
The term “haloalkyl,” as used herein, alone or in combination, refers to an alkyl radical having the meaning as defined above wherein one or more hydrogens are replaced with a halogen. Specifically embraced are monohaloalkyl, dihaloalkyl, polyhaloalkyl, and perhaloalkyl radicals. A monohaloalkyl radical, for one example, may have an iodo, bromo, chloro or fluoro atom within the radical. Dihalo and polyhaloalkyl radicals may have two or more of the same halo atoms or a combination of different halo radicals. Examples of haloalkyl radicals include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, dichlorofluoromethyl, difluoroethyl, difluoropropyl, dichloroethyl and dichloropropyl. “Haloalkylene” refers to a haloalkyl group attached at two or more positions. Examples of haloalkyl radicals include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, dichlorofluoromethyl, difluoroethyl, difluoropropyl, dichloroethyl and dichloropropyl. “Haloalkylene” refers to a haloalkyl group attached at two or more positions. Examples include fluoromethylene (—CFH—), difluoromethylene (—CF2—), chloromethylene (—CHCl—) and the like. The term “perhaloalkyl” as used herein, alone or in combination, refers to an alkyl group where all of the hydrogen atoms are replaced by halogen atoms. Examples include perfluoromethyl.
The term “nitro,” as used herein, alone or in combination, refers to —NO2.
The term “substituted” refers to moieties having substituents replacing a hydrogen on one or more carbons of the backbone. It will be understood that “substitution” or “substituted with” includes the implicit proviso that such substitution is in accordance with the permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this invention, the heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. Substituents can include any substituents described herein, for example, a halogen, a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), an alkoxyl, a phosphoryl, a phosphate, a phosphonate, a phosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyl, an aralkyl, or an aromatic or heteroaromatic moiety. It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain can themselves be substituted, if appropriate.
As set forth previously, unless specifically stated as “unsubstituted,” references to chemical moieties herein are understood to include substituted variants. For example, reference to an “aryl” group or moiety implicitly includes both substituted and unsubstituted variants.
It is understood that the disclosure of a compound herein encompasses all stereoisomers of that compound. As used herein, the term “stereoisomer” refers to a compound made up of the same atoms bonded by the same bonds but having different three-dimensional structures which are not interchangeable. The three-dimensional structures are called configurations. Stereoisomers include enantiomers and diastereomers.
The following examples are provided to further illustrate the methods of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.
The invention is further illustrated by the following examples, which are offered for illustrative purposes, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters, which can be changed or modified to yield essentially the same results.
General Considerations
All manipulations were performed using a combination of glovebox, high vacuum, and Schlenk techniques under an argon atmosphere. Solvents were purified and degassed by standard procedures.
1H NMR chemical shifts are reported in ppm relative to SiMe4 (δ=0) and were either referenced directly (for C6D5Br) or with respect to the protio solvent impurity (δ=7.16 for C6D5H, δ=2.08 for toluene-d8). 13C NMR spectra are reported in ppm relative to SiMe4 (δ=0) and were referenced internally with respect to the solvent (δ=128.06 for C6D6, δ=128.06 for C6D5H, δ=20.43 for toluene-d8). 7Li NMR are reported in ppm relative to LiCl (δ=0) and were obtained by using the Ξ/100% value of 38.863797. 19F NMR chemical shifts are reported in ppm relative to CFCl3 (δ=0.0) and were obtained by using the Ξ/100% value of 94.094011. 29Si NMR chemical shifts are reported in ppm relative to SiMe4 (δ=0.0) and were obtained by using the Ξ/100% value of 19.867187. 11B NMR chemical shifts are reported in ppm relative to BF3.OEt2 and were obtained by using the Ξ/100% value of 32.083974. Coupling constants are given in hertz. Infrared spectra were recorded on a Perkin Elmer Spectrum Two spectrometer in attenuated total reflectance (ATR) mode, or a Thermo Scientifc Nicolet FT-IR 6700 spectrometer with a liquid N2 cooled MCT-A detector, and are reported in reciprocal centimeters.
1-isopropylbenzimidazole, HC(SiMe2Cl)3, Me2Mg, [Me3PCuCl]4, [TismPr
X-Ray Structure Determinations
X-ray diffraction data were collected on a Bruker Apex II diffractometer. The structures were solved by using direct methods and standard difference map techniques, and were refined by full-matrix least-squares procedures on F2 with SHELXTL (Version 2014/7).
The synthesis of multidentate ligands and various metal complexes and their derivatives are described below in detail.
The volatile components of a solution of MeLi in Et2O (56.8 mmol, 35.5 mL of 1.6 M) were removed in vacuo and the solid obtained was dissolved in THF (ca 50 mL). The solution was treated slowly with distilled 1-isopropylbenzimidazole (8.81 g, 55 mmol) over a period of 10 minutes, and stirred for an additional 20 minutes. After this period, the volatile components were removed in vacuo to give an orange oil. Pentane (ca 30 mL) was added and the mixture was stirred for 10 minutes, after which period the volatile components were removed in vacuo to afford a light orange foam-like solid. The solid was dissolved in benzene (ca 30 mL) and the solution was added to a glass pressure vessel containing solid MeLi as obtained by the removal of volatile components in vacuo from a solution of MeLi in Et2O (18.9 mmol, 11.8 mL of 1.6 M). The resulting orange suspension was placed in an ice bath and was treated slowly with a solution of freshly distilled HC(SiMe2Cl)3 (5.4 g, 18.4 mmol) in benzene (ca 20 mL) over a period of ca. 15 minutes. The mixture was allowed to warm to room temperature and stirred until gas evolution ceased (ca 1 hour), after which period the vessel was sealed and stirred at 100° C. for 15 hours. Benzene (ca 40 mL) was added to the resulting red mixture, and the fine precipitate was allowed to settle and the solution was decanted. This process was repeated with two portions of benzene (ca 40 mL) and the combined extracts were concentrated in vacuo to a volume of ca 20 mL, thereby resulting in the deposition of a solid over a period of two days. The solid was isolated by filtration, washed with Et2O (2×ca 20 mL), and dried in vacuo to afford [TismPr
1H NMR (C6D6):
0.63 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
1.23 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
4.84 [sept, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
7.06 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
7.28 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
8.00 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi].
13C NMR (C6D6):
6.23 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
21.18 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
49.40 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
112.73 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
119.78 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
121.91 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
121.96 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
134.21 [s, 30, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
145.52 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
169.31 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CLi].
29Si NMR (C6D6): −14.48 [s, (C6H4N2CH(CH3)2CSi(CH3)2)3CLi].
7Li NMR (C6D6): 5.32.
Anal. calc. for [TismPr
IR Data (cm−1): 3053 (w), 2964 (w), 2949 (w), 1463 (m), 1389 (w), 1371 (w), 1341 (m), 1320 (w), 1282 (m), 1159 (w), 1106 (w), 1061 (m), 964 (vs), 821 (s), 791 (s), 737 (vs), 672 (s).
H2O (40 μL, 2.22 mmol) was added to a solution of [TismPr
1H NMR (C6D6):
0.55 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
1.40 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
2.30 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
5.09 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
7.14-7.23 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
7.38 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
8.04 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CH].
13C{1H} NMR (C6D6):
−1.22 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
1.89 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
21.49 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
49.85 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
112.69 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
121.13 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
121.73 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
122.49 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
134.84 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
146.98 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH],
159.75 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CH].
29Si NMR (C6D6): −7.32 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CH].
IR Data (cm−1): 2979 (w), 1459 (m), 1394 (w), 1340 (s), 1321 (m), 1266 (m) 1162 (w), 1131 (w) 1105 (w), 1060 (m), 1014 (m), 834 (s), 820 (vs), 775 (s), 740 (vs), 681 (vs).
A solution of [TismPr
A solution of [TismPr
1H NMR (C6D6):
0.20 [s, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
0.45 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
1.16 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
4.66 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
7.01-7.19 [m, 9H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
8.83 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3].
13C{1H} NMR (C6D6):
0.57 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
4.54 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
21.01 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
50.09 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
112.24 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
122.54 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
122.69 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
122.90 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
134.55 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
144.78 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
166.94 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3].
29Si NMR (C6D6): −12.69 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH3].
Anal. calc. for [TismPr
IR Data (ATR, cm−1): 2973 (m), 1462 (m), 1391 (w), 1340 (m), 1257 (m), 1060 (m), 1011 (m), 948 (s), 821 (vs), 739 (vs), 676 (s).
A solution of [TismPr
1H NMR (C6D6):
0.31 [s, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnC
0.76 [s, 18H, (C6H4N2CH(CH3)2CSi(C
1.14 [d, J=6.9 Hz, 18H, (C6H4N2CH(C
4.70 [sept, J=7 Hz, 3H (C6H4N2C
7.05 [m, 3H, (C6
7.23 [d, J=8.2 Hz, (C6
8.22 [d, J=8 Hz, (C6
13C NMR (C6D6):
−10.51 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
4.98 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
21.15 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
49.97 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
112.92 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
119.85 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
122.38 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
122.50 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
134.68 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
144.59 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
166.41 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3].
29Si NMR (C6D6): −7.97 [s, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnCH3].
Anal. calc. for [k3-TismPr
IR Data (cm−1): 2969 (w), 2896 (w), 1464 (m), 1390 (m), 1371 (m), 1354 (m), 1290 (w), 1252 (m), 1132 (w), 1066 (m), 919 (s), 890 (s), 813 (s), 739 (vs), 698 (m), 645 (m).
A solution of [(Me3P)CuCl]4 (16 mg, 0.023 mmol) in benzene (ca. 1.5 mL) was treated with [TismPr
1H NMR (C6D6):
0.58 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
1.23 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
4.77 [sept, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
7.02 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
7.11 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
7.26 [d, J=8.1 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
8.29 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu].
13C NMR (C6D6):
5.65 (6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
21.24 [6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
49.64 [3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
112.64 [3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
120.21 [3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
121.91 [30, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
122.02 [3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
134.13 [3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
144.34 [3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
168.12 [3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CCu].
29Si NMR (C6D6): −14.90 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CCu].
Anal. calc. for [TismPr
IR Data (cm−1): 3053 (w), 2963 (w), 1463 (m), 1389 (w), 1372 (w), 1344 (m), 1321 (w), 1286 (w), 1249 (m), 1159 (w), 1133 (w), 1105 (m), 954 (vs), 822 (s), 791 (s), 738 (vs), 669 (m).
A mixture of [TismPr
1H NMR (C6D6): 1.53 [bs], 4.85 [bs], 5.59 [bs], 8.09 [bs], 10.21 [bs], 22.52 [bs], 29.88 [bs]. Anal. calc. for [TismPr
IR Data (cm−1): 2972 (w), 2943 (w), 2877 (w), 1466 (m) 1392 (m), 1363 (m), 1252 (m), 1158 (w), 1133 (w), 1068 (m), 933 (s), 896 (s), 829 (s), 815 (s), 766 (m), 737 (vs), 695 (m).
Two preparation methods were employed:
(i) A solution of [TismPr
(ii) A solution of [TismPr
Anal. calcd. for [TismPr
1H NMR (C6D6):
0.40 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
1.20 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
4.67 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
7.04 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
7.19 [d, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
7.22 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
9.97 [dd, J=8 Hz, J=3 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF].
13C{1H} NMR (C6D6):
4.85 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
21.14 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
50.03 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
111.79 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
122.97 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
123.06 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
124.07 [d, J=15 Hz, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
134.02[s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
145.14 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
167.53 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF],
not observed [(C6H4N2CH(CH3)2CSI(CH3)2)3CMgF].
29Si NMR (C6D6): −12.18 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF].
19F NMR (C6D6): −152.4 [s, 1F, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgF].
IR Data (ATR, cm−1): 1356 (m), 943 (vs), 825 (s), 790 (s), 742 (vs), 697 (m), 675 (m), 530 (m), 497 (m), 436 (m).
Two preparation methods were employed:
(i) A solution of [TismPr
(ii) A solution of [TismPr
1H NMR (C6D6):
0.36 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
1.13 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
4.59 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
7.02 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
7.13 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
9.92 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl].
13C{1H} NMR (C6D6):
4.25 [s, 60, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
20.97 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
50.21 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
111.92 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
122.80 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
123.02 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
124.53 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
134.32 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
144.69 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
166.83 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl].
29Si NMR (C6D6): −12.19 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCl].
IR Data (ATR, cm−1): 1358 (m), 939 (s), 826 (s), 814 (s), 790 (m), 741 (vs), 695 (m), 559 (m), 531 (m), 440 (m).
Two preparation methods were employed:
(i) A solution of [TismPr
(ii) A solution of [TismPr
Anal. calcd. for [TismPr
1H NMR (C6D6):
0.35 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
1.12 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
4.57 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
7.01 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
7.10 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
7.14 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
9.94 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr].
13C{1H} NMR (C6D6):
4.13 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
20.94 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
50.28 [s, 3C, (C6H4N2CH(CH3)2CSI(CH3)2)3CMgBr],
111.94 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
122.64 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
123.08 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
124.79 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
134.42 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
144.48 [s, 3C, (C6H4N2CH(CH3)2CSI(CH3)2)3CMgBr],
166.63 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr].
29Si NMR (C6D6): −12.13 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgBr].
IR Data (ATR, cm−1): 1358 (w), 939 (m), 826 (m), 813 (m), 790 (w), 741 (s), 695 (w), 560 (w), 531 (w), 442 (w).
Two preparation methods were employed:
(i) A solution of [TismPr
(ii) A solution of [TismPr
1H NMR (C6D6):
0.34 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
1.10 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
4.55 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
6.99 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
7.11 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
9.86 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI].
13C{1H} NMR (C6D6):
4.21 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
20.92 [s, 6C, (C61-14N2CH(CH3)2CSi(CH3)2)3CMgI],
50.34 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
112.04 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
122.33 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
123.15 [s, 3C, (C61-14N2CH(CH3)2CSi(CH3)2)3CMgI],
124.97 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
134.53 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
144.05 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
166.32 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgI].
29Si NMR (C6D6): −11.81 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgI].
IR Data (ATR, cm−1): 1358 (w), 939 (s), 825 (vs), 791 (m), 741 (vs), 695 (m), 650 (m), 634 (m), 560 (m), 530 (m), 443 (m).
Two preparation methods were employed:
(i) A solution of [TismPr
(ii) A solution of [TismPr
1H NMR (C6D6):
−1.07 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
0.38 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
1.13 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
7.00 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
7.08 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
7.14 [d, J=2 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
9.65 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH].
13C{1H} NMR (C6D6):
4.32 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
20.96 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
50.22 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
112.06 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
122.64 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
123.00 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
124.11 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
134.44 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
144.52 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH],
166.61 [s, 3C, (C61-14N2CH(CH3)2CSi(CH3)2)3CMgSH],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH].
29Si NMR (C6D6): −12.17 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSH].
IR Data (ATR, cm−1): 1358 (w), 1254 (w), 1064 (w), 942 (m), 826 (s), 790 (m), 741 (vs), 695 (w), 675 (w), 438 (m).
Two preparation methods were employed:
(i) A solution of [TismPr
(ii) A solution of [TismPr
Anal. calcd. for [TismPr
1H NMR (C6D6):
0.41 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
1.18 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
4.44 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
4.66 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
6.31 [t, J=7 Hz, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
6.61 [d, J=7 Hz, 2H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
6.98 [m, 8H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
7.14 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
8.86 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph].
13C{1H} NMR (C6D6):
4.57 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
21.05 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
50.20 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
108.99 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
112.05 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
116.99 [s, 2C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
122.74 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
122.96 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
123.07 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
129.13 [s, 2C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
134.20 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
144.19 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
161.85 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
167.09 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph].
29Si NMR (C6D6): −12.13 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgN(H)Ph].
IR Data (ATR, cm−1): 2917 (w), 2849 (w), 1603 (w), 1524 (m), 1499 (w), 1462 (m), 1397 (w), 1340 (w), 1266 (w), 1133 (w), 1061 (w), 1011 (w), 948 (w), 821 (s), 741 (vs), 692 (m), 505 (m), 431 (m).
A solution of [TismPr
Anal. calcd. for [TismPr
1H NMR (C6D6):
0.72 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
1.08 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
2.04 [s, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
4.68 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
6.94 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
7.06 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
7.22 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
9.15 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3].
13C{1H} NMR (C6D6):
6.95 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
20.97 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
23.42 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
49.59 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
112.47 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
121.52 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
122.34 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
122.39 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
134.15 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
144.19 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
165.91 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
183.12 [s, 10, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3].
29Si NMR (C6D6): −10.37 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)CH3].
IR Data (ATR, cm−1): 3056 (w), 3000 (w), 2974 (w), 2942 (w), 2896 (w), 1534 (m), 1464 (m), 1356 (m), 940 (s), 906 (s), 828 (m), 816 (m), 795 (m), 741 (s), 684 (m), 675 (m), 506 (m).
A solution of [TismPr
1H NMR (C6D6):
0.58 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
1.16 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
2.89 [s, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
4.67 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
6.96 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
7.13 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
9.03 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3].
1H NMR (C7D8):
0.52 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
1.21 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
2.78 [s, 3H, (C6H4N2CH(CH3)2CSI(CH3)2)3CMgSC(S)CH3],
4.68 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
6.95 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
7.08 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
7.12 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
8.85 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3].
13C{1H} NMR (C7D8):
5.77 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
20.99 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
45.75 [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
50.02 [s, 3C, (C6H4N2CH(CH3)2CSI(CH3)2)3CMgSC(S)CH3],
112.24 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
122.15 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
122.37 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
122.54 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
134.29 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
144.10 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
166.63 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
not observed [s, 1C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3].
29Si NMR (C7D8): −11.37 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgSC(S)CH3].
IR Data (ATR, cm−1): 3051 (w), 2972 (w), 2939 (w), 2892 (w), 1462 (w), 1391 (w), 1372 (w), 1353 (w), 1151 (w), 1133 (w), 1065 (w), 926 (s), 891 (s), 846 (w), 826 (m), 812 (m), 793 (s), 760 (w), 737 (s), 695 (w), 679 (w), 502 (w), 488 (w), 439 (w).
A solution of PhSiH3 (9 μL, 0.073 mmol) in C6D6 (ca 0.7 mL) was added to [TismPr
1H NMR (C6D6):
0.43 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
1.18 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
4.68 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
6.78 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
7.03 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
7.18 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
9.89 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH].
13C{1H} NMR (C6D6):
4.80 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
21.11 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
50.04 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
112.03 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
122.49 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
122.76 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
123.52 [s, 30, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
134.31 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
145.22 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
167.17 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgH].
29Si NMR (C6D6): −12.49 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgH].
IR Data (FT-IR, cm−1): 3057 (w), 2974 (m), 2941 (m), 2894 (w), 1465 (m), 1391 (w), 1371 (w), 1356 (m), 1323 (w), 1302 (w), 1282 (w), 1252 (m), 1066 (m) 1012 (w), 949 (s), 827 (s), 790 (m), 746 (s).
Three preparation methods were employed:
(i) A solution of [TismPr
(ii) A solution of [TismPr
(iii) A solution of [TismPr
1H NMR (C6D6):
0.56 [s, 9H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
0.59 [s, 9H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
1.04 [d, J=7 Hz, 9H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
1.09 [d, J=7 Hz, 9H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
2.03 [d, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
2.64 [q, J=7 Hz, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
4.58 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
6.91 [t, 8 Hz, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
6.92 [t, 8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
7.06 [d, 9 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
7.11 [t, 8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
7.13 [d, 8 Hz, 2H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
7.30 [t, 8 Hz, 2H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph].
7.87 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph].
13C{1H} NMR (C6D6):
6.52 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
6.76 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
19.84 [s, 10, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
20.89 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
21.07 [s, 3C, (C61-14N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
33.87 [s, 10, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
49.65 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
112.46 [s, 3C, (C61-14N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
115.51 [s, 10, (C6F14N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
120.98 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
122.30 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
122.58 [s, 3C, (C61-14N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
123.16 [s, 2C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
133.78 [s, 30, (C61-14N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
143.73 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
162.35 [s, 10, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
165.12 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph],
not observed [(C61-14N2CH(CH3)2CSI(CH3)2)3CMgCH(Me)Ph],
2C obscured by solvent [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph].
29Si NMR (C6D6): −10.31 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgCH(Me)Ph].
IR Data (ATR, cm−1): 2973 (w), 1605 (w), 1460 (m), 1392 (w), 1370 (w), 1339 (m), 1323 (w), 1266 (w), 1158 (w), 1132 (w), 1104 (w), 1060 (m), 1010 (w), 948 (w), 820 (vs), 779 (s), 739 (vs), 696 (m), 649 (m), 540 (m), 499 (m), 430 (m).
A mixture of ZnBr2 (115 mg, 0.511 mmol) and [TismPr
Anal. calcd. for [k3-TismPr
1H NMR (C6D6):
0.77 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
1.12 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
4.65 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
7.04 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
7.17 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
8.55 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr].
13C{1H} NMR (C6D6):
4.72 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
21.09 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
50.29 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
112.94 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
120.21 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
122.82 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
122.94 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
134.58 [s, 3C, (C6H4N2CH(CH3)2CSI(CH3)2)3CZnBr],
143.88 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
165.99 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr].
29Si NMR (C6D6): −6.75 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnBr].
IR Data (ATR, cm−1): 2974 (w), 1463 (w), 1390 (w), 1367 (w), 1323 (w), 1293 (w), 1255 (w), 1068 (w), 881 (s), 830 (s), 814 (s), 798 (m), 766 (w), 740 (s), 695 (w), 652 (w), 564 (w).
A mixture of [TismPr
Anal. calcd. for [k3-TismPr
1H NMR (C6D6):
0.81 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
1.14 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
4.72 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
5.53 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
7.05 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
7.15 [m, 3H, (C6H4N2CH(CH3)2CSI(CH3)2)3CZnH],
7.23 [d, J=9 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
8.24 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH].
13C{1H} NMR (C6D6):
5.03 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
21.17 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
50.04 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
112.88 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
119.96 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
122.41 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
122.54 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
134.58 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
144.53 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
166.62 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CZnH].
29Si NMR (C6D6): −7.70 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnH].
IR Data (ATR, cm−1): 2972 (w), 1681 (w), 1463 (w), 1390 (w), 1356 (w), 1330 (w), 1290 (w), 1250 (w), 1160 (w), 1132 (w), 1066 (w), 918 (m), 889 (s), 828 (s), 813 (s), 798 (s), 765 (m), 737 (vs), 684 (w), 647 (w), 561 (w), 498 (s), 465 (m), 429 (w).
A solution of [κ3-TismPr
1H NMR (C6D6):
0.27 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
1.12 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
4.46 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
6.97 [m, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
7.10 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
7.78 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
not observed [1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3].
1H NMR (C6D5Br):
0.29 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
1.35 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3),
4.58 (sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
7.15 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
7.23 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
7.36 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
7.90 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
not observed [1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3].
13C{1H} NMR (C6D5Br):
3.38 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
20.92 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
51.25 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
113.77 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
116.87 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
124.24 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
124.41 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
133.44 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
140.48 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
167.09 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
not observed/obscured by solvent [(C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3].
19F NMR (C6D5Br):
−166.22 [meta, m, 6F, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
−163.59 [para, t, J=21 Hz, 3F, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3],
−131.84 [ortho, d, J=22 Hz, 6F, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3].
29Si NMR (C6D5Br): −4.48 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3].
11B NMR (C6D5Br):
−24.5 [d, J=95 Hz, 1B, (C6H4N2CH(CH3)2CSi(CH3)2)3CZnHB(C6F5)3].
IR Data (ATR, cm−1): 2975 (w), 1639 (w), 1508 (m), 1460 (s), 1403 (w), 1371 (m), 1317 (w), 1298 (w), 1274 (w), 1260 (w), 1163 (w), 1102 (m), 1068 (m), 968 (s), 922 (vs), 827 (s), 813 (m), 790 (m), 764 (m), 745 (s), 700 (w), 678 (vs), 659 (m), 601 (w), 564 (m), 530 (w), 467 (w), 444 (w), 434 (w), 405 (w).
A solution of [TismPr
Anal. calcd. for [TismPr
1H NMR (C6D6):
0.68 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
1.10 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
4.68 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
6.94 [t, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
7.08 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
7.19 [t, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
8.87 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
9.06 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H].
13C{1H} NMR (C6D6):
6.69 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
21.00 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
49.69 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
112.45 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
121.55 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
122.46 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
122.52 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
134.13 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
144.02 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
166.06 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
173.24 [s, 10, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H],
not observed [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H].
29Si NMR (C6D6): −10.36 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgOC(O)H].
IR Data (ATR, cm−1): 1577 (m), 1465 (w), 1393 (w), 1356 (w), 1329 (w), 1248 (w), 1067 (w), 939 (s), 905 (s), 828 (m), 815 (m), 795 (m), 764 (w), 741 (s), 686 (m), 502 (m), 444 (w).
A solution of [TismPr
1H NMR (C6D6):
0.30 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F6)3],
1.18 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F5)3],
4.55 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F5)3],
7.00 [t, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F5)3],
7.11 [m, 6H, obscured by solvent, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F5)3],
7.73 [d, J=8 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F6)3],
not observed [1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F5)3].
19F NMR (C6D6):
−166.00 [meta, br, 6F, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F6)3],
−163.49 [para, br, 3F, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F6)3],
−131.30 [ortho, br, 6F, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgHB(C6F5)3].
IR Data (ATR, cm−1): 2946 (w), 1639 (w), 1508 (w), 1461 (s), 1405 (w), 1360 (m), 1319 (w), 1276 (w), 1260 (w), 1161 (w), 1064 (m), 968 (m), 940 (vs), 826 (s), 813 (s), 791 (m), 735 (s), 696 (w), 683 (w), 649 (w), 621 (w), 561 (w), 543 (w), 531 (w), 502 (w), 443 (m).
Three preparation methods were employed:
(i) A suspension of [TismPr
(ii) A suspension of {[TismPr
(iii) A suspension of [TismPr
1H NMR (C6D6):
0.27 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
1.10 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
4.50 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
7.02 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
7.13 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
8.27 [d, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
8.76 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3].
1H NMR (C6D5Br):
0.24 [s, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
1.30 [d, J=7 Hz, 18H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
4.64 [sep, J=7 Hz, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
7.08 [m, 6H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
7.26 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
8.14 [m, 3H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
8.73 [s, 1H, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3].
13C{1H} NMR (C6D5Br):
3.95 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
20.78 [s, 6C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
50.16 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
112.58 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
119.40 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
122.72 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
123.10 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
133.56 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
142.60 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
167.38 [s, 3C, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
170.84 [s, 10, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
not observed/obscured by solvent [(C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3].
19F NMR (C6D5Br):
−163.4 [meta, m, 6F, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
−157.6 [para, t, J=21 Hz, 3F, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3],
−132.6 [ortho, m, 6F, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3].
29Si NMR (C6D5Br): −10.71 [s, 3Si, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3].
11B NMR (C6D5Br): −6.97 [b, 1B, (C6H4N2CH(CH3)2CSi(CH3)2)3CMgO(H)COB(C6F5)3].
IR Data (ATR, cm−1): 2945 (w), 1665 (s), 1645 (m), 1515 (m), 1461 (vs), 1387 (m), 1373 (s), 1357 (m), 1321 (s), 1280 (m), 1259 (m), 1160 (m), 1135 (w), 1095 (s), 1067 (m), 981 (s), 969 (s), 943 (vs), 916 (vs), 825 (vs), 812 (vs), 791 (s), 783 (s), 775 (m), 764 (m), 751 (vs), 739 (vs), 685 (s), 674 (vs), 616 (m), 602 (m), 577 (m), 560 (s), 531 (m), 514 (m), 498 (m), 443 (s).
A general route to obtain the Markovnikov product, Ph(Me)C(H)SiH2Ph, by the hydrosilylation of styrene using [TismPr
(i) A solution of phenylsilane (15 equiv, 0.107 mmol) and styrene (10 equiv, 0.071 mmol) in C6D6 (0.7 mL), with mesitylene (2 equiv, 0.014 mmol) as an internal standard, was added to [TismPr
(ii) A solution of phenylsilane (15 equiv, 0.044 mmol) and styrene (10 equiv, 0.029 mmol) in C6D6 (0.7 mL) was added to [TismPr
A general route to obtain the Markovnikov product, Ph(Me)C(H)Bpin, by the hydroboration of styrene using [TismPr
(i) A solution of pinacolborane (15 equiv, 0.107 mmol) and styrene (10 equiv, 0.071 mmol) in C6D6 (0.7 mL), with mesitylene (2 equiv, 0.014 mmol) as an internal standard, was added to [TismPr
(ii) A solution of pinacolborane (15 equiv, 0.044 mmol) and styrene (10 equiv, 0.029 mmol) in C6D6 (0.7 mL) was added to [TismPr
The catalytic cycle for the hydrosilylation of CO2 by magnesium or zinc system is summarized below (Scheme 3). Exemplary preparations are also provided. Selected results are shown in Table 1.
Magnesium System:
(a) A solution of PhSiH3 (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(b) A solution of Et3SiH (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(c) A solution of Ph3SiH (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(d) A solution of PhSiH3 (1.42 mmol), [TismPr
(e) A solution of Et3SiH (1.42 mmol), [TismPr
(f) A solution of Ph3SiH (1.42 mmol), [TismPr
(g) A solution of PhSiH3 (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(h) A solution of Et3SiH (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(i) A solution of Ph3SiH (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(j) A solution of PhSiH3 (1.42 mmol), [TismPr
(k) A solution of Et3SiH (1.42 mmol), [TismPr
(I) A solution of Ph3SiH (1.42 mmol), [TismPr
(m) A solution of PhSiH3 (0.14 mmol) in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
Zinc System:
(a) A solution of PhSiH3 (0.037 mmol) and mesitylene in C6D5Br (ca 0.5 mL) was added to a mixture of {[TismPr
(b) A solution of Et3SiH (0.014 mmol) and mesitylene in C6D5Br (ca 0.5 mL) was added to a mixture of {[TismPr
(c) A solution of Ph3SiH (0.014 mmol) and mesitylene in C6D5Br (ca 0.5 mL) was added to a mixture of {[TismPr
(d) A solution of PhSiH3 (0.11 mmol) in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
a[Mg] = [TismPr
bNumber of Si—H bonds consumed per metal.
cC6D6.
dValues for [TismPr
eC6D5Br.
A general route to obtain a formaldehyde equivalent from CO2 using the metal complexes disclosed herein as catalyst is illustrated below (Scheme 4). Detailed preparation is also provided.
Exemplary procedures are provided below.
(a) A solution of Ph3SiH (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(b) A solution of Ph3SiH (1.42 mmol), [TismPr
(c) A solution of Ph3SiH (0.14 mmol) and mesitylene in C6D6 (ca 0.5 mL) was added to a mixture of [TismPr
(d) A solution of Ph3SiH (1.42 mmol), [TismPr
A catalyst is treated with carbon monoxide (1 atm) and 10-1000 equivalents of a hydrosilane (R3SiH) or hydroborane (R2BH), resulting in the catalytic formation of the reduced species.
A catalyst is treated with hydrogen (1-20 atm) and 10-1000 equivalents of an alkene or alkyne, resulting in the catalytic formation of the hydrogenated species.
A catalyst is treated with an alkene (10-1000 equivalents), resulting in the catalytic formation of the polymerized species.
A catalyst is treated with an alcohol or primary or secondary amine (10-1000 equivalents) and 10-1000 equivalents of a hydrosilane (R3SiH) or hydroborane (R2BH), resulting in the catalytic formation of hydrogen.
A catalyst is treated with a ketone or aldehyde (10-1000 equivalents) and 10-1000 equivalents of a hydrosilane (R3SiH) or hydroborane (R2BH), resulting in the catalytic formation of the corresponding hydrosilylated or hydroborated products.
A catalyst is treated with an aldehyde (10-1000 equivalents), resulting in the catalytic formation of the corresponding ester.
A catalyst is treated with carbon dioxide (1-20 atm) and hydrogen (1-20 atm) resulting in the catalytic formation of a hydrogenated species such as, e.g., methanol, formic acid, methane, formaldehyde, etc.
A catalyst is treated with carbon monoxide (1-20 atm) and hydrogen (1-20 atm) resulting in the catalytic formation of a hydrogenated species such as, e.g., methanol, formic acid, methane, formaldehyde, etc.
Four Appendices (A to D) are attached hereto which provide additional details regarding the inventive principles described in this disclosure. The Appendices are expressly incorporated herein by reference in their entireties. In the event of a conflict between the teachings of this application and those of the incorporated Appendices, the teachings of this application control.
All documents cited in this application are hereby incorporated by reference as if recited in full herein.
Although illustrative embodiments of the present invention have been described herein, it should be understood that the invention is not limited to those described, and that various other changes or modifications may be made by one skilled in the art without departing from the scope or spirit of the invention.
The present application claims benefit of U.S. Provisional patent Application Ser. No. 62/646,062, filed on Mar. 21, 2018 which application is incorporated by reference herein in its entirety.
This invention was made with government support under grant nos. CHE-1058987 and CHE-1465095, awarded by NSF, and grant no. DE-FG02-93ER14339, awarded by Department of Energy (DOE). The government has certain rights in the invention.
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| Number | Date | Country | |
|---|---|---|---|
| 20190291088 A1 | Sep 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62646062 | Mar 2018 | US |
