Hypercoordinating Stannanes with C,N-Donor Ligands: A Structural, Computational, and Polymerization Study
Year: 2025
Type: article
Abstract: Select triphenyl stannanes bearing either a formally sp2 or sp3 hybridized amine, viz 2-(pyC2H4)SnPh3 (2: py = pyridinyl), 4-(pyC2H4)SnPh3 (3), 2-(pzC2H4)SnPh3 (4: pz = pyrazyl), and Me2N(CH2)3SnPh3 (6), were prepared and characterized by NMR spectroscopy (119Sn, 13C, 1H), and additionally, in the case of 2, by single crystal X-ray diffraction. Bromination of 2 to yield 2-(pyC2H4)SnPhBr2 (8) was achieved in good yield. X-ray crystallographic analysis of 8 revealed two unique molecules with 5-coordinate Sn centers featuring Sn-N distances of 2.382 (5) and 2.363 (5) Å, respectively. The calculated structures of the non- and hypercoordinating C,N-stannanes (1–9) were in good agreement with available crystallographic data. The relative stabilities of hyper- and non-hypercoordinating conformers obtained from conformational sampling were determined by comparison with reference conformers and by natural bond orbital (NBO) energetic analyses. Reduction of 8 to the dihydride species, 2-(pyC2H4)SnPhH2 (9), and subsequent conversion to the polystannane, -[2-(pyC2H4)SnPh]n- (15), by transition metal-catalyzed dehydropolymerization was also achieved. Evidence for the decomposition of 15 into a redistributed distannoxane, {2-(pyC2H4)SnPh2}2O (16), was also observed.
Source: Figshare
Authors: Gloria M D’Amaral (20898083), Desiree N Bender (20898086), Nicola Piccolo (20898065), Alan J Lough (10842351), Robert A Gossage (10842006), Daniel A Foucher (20898089), R Stephen Wylie (20898092)
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7010369697
FWCI:
Cites:
Cited by:
Related to: