Issue 16, 2021

Oxidative addition of cyanogen bromide to C,N-chelated and Lappert's stannylenes

Abstract

Stannylenes of L2Sn type bearing either C,N-chelating (1, L = LCN = 2-(N,N-dimethylaminomethyl)phenyl) or bulky amido (2, L = LN = N(SiMe3)2) ligands react with cyanogen bromide (Br–C[triple bond, length as m-dash]N) via an oxidative-addition reaction to give monomeric six-coordinate (LCN)2Sn(Br)CN (1a) and four-coordinate (LN)2Sn(Br)CN (2a) stannanes in moderate yields. In solution, both 1a and 2a undergo instantaneous bromido-cyanido ligand redistribution reactions, leading to mixtures containing 1a, (LCN)2SnBr2 (1b) and (LCN)2Sn(CN)2 (1c) or 2a, (LN)2SnBr2 (2b) and (LN)2Sn(CN)2 (2c), respectively. The prepared species were characterised by multinuclear NMR spectroscopy in solution (1a–c and 2a–c) and in the solid state (1a–c). The crystal structures of 1a/b/c, 2a/b/c and sole 2b were determined by XRD analyses. DFT calculations and QTAIM analysis were also carried out to corroborate the experimental results.

Graphical abstract: Oxidative addition of cyanogen bromide to C,N-chelated and Lappert's stannylenes

Supplementary files

Article information

Article type
Paper
Submitted
02 Mar 2021
Accepted
16 Mar 2021
First published
17 Mar 2021

Dalton Trans., 2021,50, 5519-5529

Oxidative addition of cyanogen bromide to C,N-chelated and Lappert's stannylenes

P. Švec, M. A. Samsonov, Z. Růžičková, J. Brus and A. Růžička, Dalton Trans., 2021, 50, 5519 DOI: 10.1039/D1DT00704A

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