Group 14 Metal Terminal Phosphides: Correlating Structure with |JMP|

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• 作者：Eric C. Y. Tam ; Nicola A. Maynard ; David C. Apperley ; J. David Smith ; Martyn P. Coles ; J. Robin Fulton
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：September 3, 2012
• 年：2012
• 卷：51
• 期：17
• 页码：9403-9415
• 全文大小：563K
• 年卷期：v.51,no.17(September 3, 2012)
• ISSN：1520-510X

文摘

A series of heavier group 14 element, terminal phosphide complexes, M(BDI)(PR₂) (M = Ge, Sn, Pb; BDI = CH{(CH₃)CN-2,6-iPr₂C₆H₃}₂; R = Ph, Cy, SiMe₃) have been synthesized. Two different conformations (endo and exo) are observed in the solid-state; the complexes with an endo conformation have a planar coordination geometry at phosphorus (M = Ge, Sn; R = SiMe₃) whereas the complexes possessing an exo conformation have a pyramidal geometry at phosphorus. Solution-state NMR studies reveal through-space scalar coupling between the tin and the isopropyl groups on the N-aryl moiety of the BDI ligand, with endo and exo exhibiting different J_SnC values. The magnitudes of the tin鈥損hosphorus and lead鈥損hosphorus coupling constants, |J_SnP| and |J_PbP|, differ significantly depending upon the hybridization of the phosphorus atom. For Sn(BDI)(P{SiMe₃}₂), |J_SnP| is the largest reported in the literature, surpassing values attributed to compounds with tin鈥損hosphorus multiple-bonds. Low temperature NMR studies of Pb(BDI)(P{SiMe₃}₂) show two species with vastly different |J_PbP| values, interpreted as belonging to the endo and exo conformations, with spp>2p>- and spp>3p>-hybridized phosphorus, respectively.