A trapped silicon atom: The compound (L:)2Si with low-valent silicon was synthesized from its dichloride biradical precursor (L:)2SiCl2 by reduction with KC8. Theoretical analysis suggest that there are two donor–acceptor σ bonds L:→Si←:L. There is one σ lone-pair orbital at Si and one π orbital which features significant π-back-donation L:←Si→:L giving short SiC bonds.

Kartik Chandra Mondal

Department Of Chemistry

W. Roesky Herbert

C. Schwarzer Martin

Frenking Gernot

Niepötter Benedikt

Wolf Hilke

Herbst-Irmer Regine

Stalke Dietmar

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Angewandte Chemie

Herein, we report the synthesis and characterization of the metal free low valent fluoroborylene [(Me-cAAC)2BF] (1) stabilized by cyclic (alkyl)(amino) carbene (cAAC). The fluoroborylene 1 is obtained by the reductive defluorination of Me-cAAC:BF3 with 2.0 equivalents of KC8 in the presence of 1.0 equivalent of Me-cAAC. Due to its highly electron rich nature, 1 underwent one-electron oxidation with 1.0 equivalent of lithium tetrakis(pentafluorophenyl)borate [LiB(C6F5)4] to form the radical cation [(Me-cAAC)2BF]+[B(C6F5)4]- (2). DFT studies suggested that the lone pair of electrons is localized on the boron atom in 1, which explains its unprecedented reactivity. Both compounds 1 and 2 were characterized by X-ray crystallography. The radical cation 2 was studied by EPR spectroscopy.

Fulltext

Dalton Transactions

Isolation of base stabilized fluoroborylene and its radical cation

A Stable Singlet Biradicaloid Siladicarbene: (L:)2Si

Journal	Data powered by TypesetAngewandte Chemie
Publisher	Data powered by TypesetWiley Online Library
Open Access	No