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

Autor: Švec, Petr, Samsonov, Maksim A., Růηičková, Zdeňka, Brus, Jiří, Růηička, Aleš
Předmět:
Zdroj: Dalton Transactions: An International Journal of Inorganic Chemistry; 4/28/2021, p5519-5529, 11p
Abstrakt: 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≡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. [ABSTRACT FROM AUTHOR]
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