Gloria M. D'Amaral, Desiree N. Bender, Nicola Piccolo, A. Lough, Robert A. Gossage, D. Foucher, R. S. Wylie
{"title":"Hypercoordinating Stannanes with C,N-Donor Ligands: A Structural, Computational, and Polymerization Study","authors":"Gloria M. D'Amaral, Desiree N. Bender, Nicola Piccolo, A. Lough, Robert A. Gossage, D. Foucher, R. S. Wylie","doi":"10.3390/inorganics12040122","DOIUrl":null,"url":null,"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.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1000,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.3390/inorganics12040122","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
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.
期刊介绍:
Inorganics is an open access journal that covers all aspects of inorganic chemistry research. Topics include but are not limited to: synthesis and characterization of inorganic compounds, complexes and materials structure and bonding in inorganic molecular and solid state compounds spectroscopic, magnetic, physical and chemical properties of inorganic compounds chemical reactivity, physical properties and applications of inorganic compounds and materials mechanisms of inorganic reactions organometallic compounds inorganic cluster chemistry heterogenous and homogeneous catalytic reactions promoted by inorganic compounds thermodynamics and kinetics of significant new and known inorganic compounds supramolecular systems and coordination polymers bio-inorganic chemistry and applications of inorganic compounds in biological systems and medicine environmental and sustainable energy applications of inorganic compounds and materials MD