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Compounds with Alternating Single and Double Bonds of Antimony and Silicon; Isoelectronic to Ethane-1,2-diimine by Mohd Nazish; Christina M. Legendre; Nico Graw; Regine Herbst-Irmer; Shahila Muhammed; Pattiyil Parameswaran; Dietmar Stalke; Herbert W. Roesky is a Chemistry article available to read on EtoBox.

What is Compounds with Alternating Single and Double Bonds of Antimony and Silicon; Isoelectronic to Ethane-1,2-diimine about?

We present an approach for preparing chain-type unsaturated molecules with low oxidation state Si(I) and Sb(I) supported by amidinato ligands that exploit to generate heavy analogues of ethane 1,2-diimine. The reduction of antimony dihalide (R-SbCl 2 ) with KC 8 in the presence of silylene chloride afforded L(Cl)SiSbTip (1) and L(Cl)SiSb Ter Ph (2), respectively. Compounds 1 and 2 further undergo reduction with KC 8 to produce TipSbLSiLSiSbTip (3) and Ter PhSbLSiLSiSb Ter Ph (4). The solid-state structures and DFT studies show that all compounds have σ-type lone pairs at each Sb atom. It forms a strong pseudo-π-bond with Si. The pseudo-πbond is formed by the hyperconjugative donation of the π-type lone pair at Sb to the Si-N σ* MO. The quantum mechanical studies indicate that compounds 3 and 4 has delocalized pseudo-π-MOs arising from hyperconjugative interactions. Hence, 1 and 2 can be considered as isoelectronic to imine, while 3 and 4 are isoelectronic to ethane-1,2-diimine. The proton affinity studies indicate that the pseudo-πbond resulting from the hyperconjugative interaction is more reactive than the σ-type lone pair.

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Author

Mohd Nazish; Christina M. Legendre; Nico Graw; Regine Herbst-Irmer; Shahila Muhammed; Pattiyil Parameswaran; Dietmar Stalke; Herbert W. Roesky

Publisher

American Chemical Society (ACS)

Published

2023

Language

EN

Field

Chemistry (Physical Sciences)