Reactions of Lithiated Diphosphanes R2P–P(SiMe3)Li (R = tBu and iPr) with [MeNacnacTiCl2·THF] and [MeNacnacTiCl3]. Formation and Structure of TitaniumIII and TitaniumIV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

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• 作者：Ł. PonikiewskiA. Ziółkowska ; J. Pikies
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：February 6, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：1094-1103
• 全文大小：507K
• ISSN：1520-510X

文摘

β-Diketiminate complexes of Ti^III-containing phosphanylphosphido ligands [^MeNacnacTi(Cl){η²-P(SiMe₃)-PR₂}] (^MeNacnac^– = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr₂C₆H₃) were prepared by reactions of [^MeNacnacTiCl₂·THF] with lithium derivatives of diphosphanes R₂P–P(SiMe₃)Li (R = tBu, iPr) in toluene solutions. Surprisingly, reactions of [^MeNacnacTiCl₂·THF] with R₂P–P(SiMe₃)Li in THF solutions led to Ti^IV complexes containing phosphanylphosphinidene ligands [^MeNacnacTi(Cl)(η²-P-PtBu₂)] via an autoredox path involving a migration of a nitrene NAr from the Nacnac skeleton to the Ti centers. Solid-state structures of [^MeNacnacTi(Cl){η²-P(SiMe₃)-PtBu₂}] (1a) and [^MeNacnacTi(Cl)(η²-P-PtBu₂)] (two isomers 2a1, 2a2) together with [^MeNacnacTi(Cl){η²-P(SiMe₃)-PiPr₂}] (1b) and [^MeNacnacTi(Cl)(η²-P-PiPr₂)] (2b) were established by the single-crystal X-ray diffraction and display clearly side-on geometry of the (Me₃Si)P–PR₂ and P–PR₂ moieties in the solid state. Phosphanylphosphinidene complexes [^MeNacnacTi(Cl)(η²-P-PR₂)] indicate that the ³¹P NMR resonances of phosphinidene P atoms appear at a very low field in solution and in the solid state.