Hypercoordinating Stannanes with C,N-Donor Ligands: A Structural, Computational, and Polymerization Study

Select triphenyl stannanes bearing either a formally sp(2) or sp(3) hybridized amine, viz 2-(pyC(2)H(4))SnPh3 (2: py = pyridinyl), 4-(pyC(2)H(4))SnPh3 (3), 2-(pzC(2)H(4))SnPh3 (4: pz = pyrazyl), and Me2N(CH2)(3)SnPh3 (6), were prepared and characterized by NMR spectroscopy (Sn-119, C-13, H-1), and additionally, in the case of 2, by single crystal X-ray diffraction. Bromination of 2 to yield 2-(pyC(2)H(4))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) angstrom, 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-(pyC(2)H(4))SnPhH2 (9), and subsequent conversion to the polystannane, -[2-(pyC(2)H(4))SnPh](n)- (15), by transition metal-catalyzed dehydropolymerization was also achieved. Evidence for the decomposition of 15 into a redistributed distannoxane, {2-(pyC(2)H(4))SnPh2}(2)O (16), was also observed.