O-oximatosilanes: weak beta-donor interactions as secondary bonds

Losehand U, Mitzel NW (1998)
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (15): 2537-2540.

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The oximatosilanes H3SiON=CMe2, ClH2SiON=CMe2 and H2Si(ON=CMe2)(2) were prepared from the reaction of lithiated acetone oxime with bromosilane and dichlorosilane respectively. They have been characterised by NMR (H-1, C-13, N-15, O-17 and Si-29) and by gas-phase IR spectroscopy. The molecular structures of H3SiON=CMe2 and H2Si(ON=CMe2)(2) have been determined by low-temperature X-ray crystallography. Small Si-O-N angles have been detected in these structures, which are indicative of the formation of weak secondary interactions of the beta-donor-acceptor type between silicon and nitrogen atoms. Important geometrical parameters: H3SiON=CMe2, Si-O 1.673(1), N-O 1.433(1) Angstrom, Si-O-N 106.0(1)degrees, N=C 1.273(2) Angstrom; H2Si(ON=CMe2)(2), Si-O 1.657(1), 1.650(1), N-O 1.466(2), 1.447(2), N=C 1.271(2), 1.266(2) Angstrom, Si-O-N 102.5(1), 107.5(1)degrees. The geometries of H2SiON=CMe2, FH2SiON=CMe2 and ClH2SiON=CMe2 were calculated by optimisations at the MP2/6-311G** level of theory. The Si-O-N angles in FH2SiON=CMe2 and ClH2SiON=CMe2 are predicted to be smaller than that in H3SiON=CMe2. A natural bond orbital analysis describes the beta-donor interaction as weak negative hyperconjugation lp(O)-->sigma*(SiO) and lp(O)-->sigma*(SiH). In general the beta-donor bonds in oximatosilanes are found to be weaker than in the related hydroxyaminosilanes.
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Losehand U, Mitzel NW. O-oximatosilanes: weak beta-donor interactions as secondary bonds. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS. 1998;(15):2537-2540.
Losehand, U., & Mitzel, N. W. (1998). O-oximatosilanes: weak beta-donor interactions as secondary bonds. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS(15), 2537-2540.
Losehand, U., and Mitzel, N. W. (1998). O-oximatosilanes: weak beta-donor interactions as secondary bonds. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2537-2540.
Losehand, U., & Mitzel, N.W., 1998. O-oximatosilanes: weak beta-donor interactions as secondary bonds. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (15), p 2537-2540.
U. Losehand and N.W. Mitzel, “O-oximatosilanes: weak beta-donor interactions as secondary bonds”, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1998, pp. 2537-2540.
Losehand, U., Mitzel, N.W.: O-oximatosilanes: weak beta-donor interactions as secondary bonds. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS. 2537-2540 (1998).
Losehand, U, and Mitzel, Norbert W. “O-oximatosilanes: weak beta-donor interactions as secondary bonds”. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS 15 (1998): 2537-2540.
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