Silylation products of cyclic tri-aminal carbanions and their lithiation

Sicking C, Mix A, Neumann B, Stammler H-G, Mitzel NW (2012)
Dalton Transactions 41(1): 104-111.

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Abstract
The structure of 1,3,5-trimethyl-1,3,5-triaza-cyclohexane (TMTAC) was determined by single crystal X-ray diffraction and compared with earlier gas-phase data. It shows a preference for an aee-conformation in all phases. Lithiated TMTAC, [(RLi)(2)center dot(RH)] (1) (R = 2,4,6-trimethyl-2,4,6-triazacyclohex- 1-yl), was reacted with Et(3)SiCl, Ph(3)SiCl and PhMe(2)SiCl to afford the substituted silanes Et(3)SiR (1), Ph(3)SiR (2) and PhMe(2)SiR (3) in moderate yields. They were characterised by NMR spectroscopy ((1)H, (13)C, (29)Si). 1 reacts with Me(2)SiCl(2) and Ph(2)SiCl(2) to give Me(2)SiR(2) (5) and Ph(2)SiR(2) (6) which were characterised by NMR spectroscopy. 5 was also identified by crystal structure determination. Analogous triple substitution could not be observed by employing trichlorosilanes. Quantumchemical calculations explain this by sterical overcrowding of the silicon atom. The reaction of 1 with SiCl(4) did not yield fourfold substitution but a formal insertion product of SiCl(2) into a C-N bond of the TMTAC ring (2,4,6-trimethyl-2,4,6-triaza-1,1-dichloro-1-sila-cycloheptane, 7) in very small quantities. It was identified by X-ray crystallography and shows an intramolecular Si center dot center dot center dot N dative bond. The reactions of (3) and (5) with n-butyl lithium afforded lithiation of the silicon bound methyl groups in both cases. The products, 8 and 9, were characterised by NMR spectroscopy ((1)H, (13)C, (29)Si), 8 was also characterised by X-ray crystallography.
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Sicking C, Mix A, Neumann B, Stammler H-G, Mitzel NW. Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions. 2012;41(1):104-111.
Sicking, C., Mix, A., Neumann, B., Stammler, H. - G., & Mitzel, N. W. (2012). Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions, 41(1), 104-111.
Sicking, C., Mix, A., Neumann, B., Stammler, H. - G., and Mitzel, N. W. (2012). Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions 41, 104-111.
Sicking, C., et al., 2012. Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions, 41(1), p 104-111.
C. Sicking, et al., “Silylation products of cyclic tri-aminal carbanions and their lithiation”, Dalton Transactions, vol. 41, 2012, pp. 104-111.
Sicking, C., Mix, A., Neumann, B., Stammler, H.-G., Mitzel, N.W.: Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions. 41, 104-111 (2012).
Sicking, Constantin, Mix, Andreas, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. “Silylation products of cyclic tri-aminal carbanions and their lithiation”. Dalton Transactions 41.1 (2012): 104-111.
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