om010934b_si_002.pdf (827.86 kB)
Synthesis and Structure of Group 14 Element Derivatives of Carbotelluroates
journal contribution
posted on 2002-02-26, 00:00 authored by Kazuyasu Tani, Ryo Yamada, Takahiro Kanda, Masahiro Suzuki, Shinzi Kato, Toshiaki MuraiGroup 14 element derivatives of carbotelluroates, RCOTeMPh3 (M = Ge, Sn, Pb), were
synthesized as stable compounds by reacting sodium carbotelluroates with Ph3MCl and were
characterized by IR and 13C and 125Te NMR spectra. Their molecular structures were revealed
by X-ray molecular analysis. The CO···Sn distance in RCOTeSnPh3 was found to be shorter
than the CO···Ge distance in RCOTeGePh3, despite the fact that the atomic radius of Sn
is larger than that of Ge. A similar shortening of the nonbonding distance was observed for
the corresponding selenium derivatives. Molecular orbital calculations of model compounds,
i.e., CH3COEM(CH3)3 (E = Se, Te; M = Ge, Sn, Pb), at the B3LYP/LANL2DZ+p level also
supported this shortening of the CO···Sn distance. NBO (natural bond orbital) analyses
of the model compounds showed that two types of orbital interactions, nO→σ*ME and nO→σ*MC
(E = S, Se, Te; M = Ge, Sn, Pb), are important in these carbochalcogenoates. Furthermore,
the former interaction has a greater role in the case of carbothioates, whereas the latter is
dominant in carbotelluroates.