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

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 50; no. 16; pp. 5519 - 5529
• Main Authors: Švec, Petr, Samsonov, Maksim A, RůŽičková, Zdeňka, Brus, Jiří, RůŽička, Aleš
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 28.04.2021
• Subjects: Chelation; Crystal structure; Crystallography; Cyanogen; Ligands; Mathematical analysis; Molecular structure; NMR spectroscopy; Solid state; Spectrum analysis
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d1dt00704a

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.