Ponikiewski Ł, Ziółkowska A, Pikies J
Department of Inorganic Chemistry, Chemical Faculty, Gdansk University of Technology , 11/12 Gabriela Narutowicza Str, 80-233 Gdansk, Poland.
Inorg Chem. 2017 Feb 6;56(3):1094-1103. doi: 10.1021/acs.inorgchem.6b01929. Epub 2017 Jan 13.
β-Diketiminate complexes of Ti-containing phosphanylphosphido ligands [NacnacTi(Cl){η-P(SiMe)-PR}] (Nacnac = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPrCH) were prepared by reactions of [NacnacTiCl·THF] with lithium derivatives of diphosphanes RP-P(SiMe)Li (R = tBu, iPr) in toluene solutions. Surprisingly, reactions of [NacnacTiCl·THF] with RP-P(SiMe)Li in THF solutions led to Ti complexes containing phosphanylphosphinidene ligands [NacnacTi(Cl)(η-P-PtBu)] via an autoredox path involving a migration of a nitrene NAr from the Nacnac skeleton to the Ti centers. Solid-state structures of [NacnacTi(Cl){η-P(SiMe)-PtBu}] (1a) and [NacnacTi(Cl)(η-P-PtBu)] (two isomers 2a1, 2a2) together with [NacnacTi(Cl){η-P(SiMe)-PiPr}] (1b) and [NacnacTi(Cl)(η-P-PiPr)] (2b) were established by the single-crystal X-ray diffraction and display clearly side-on geometry of the (MeSi)P-PR and P-PR moieties in the solid state. Phosphanylphosphinidene complexes [NacnacTi(Cl)(η-P-PR)] indicate that the P NMR resonances of phosphinidene P atoms appear at a very low field in solution and in the solid state.
含磷膦基配体的钛β-二酮亚胺配合物[NacnacTi(Cl){η-P(SiMe)-PR}]（Nacnac = [Ar]NC(Me)CHC(Me)N[Ar]；Ar = 2,6-iPrCH）是通过[NacnacTiCl·THF]与二膦烷RP-P(SiMe)Li（R = tBu，iPr）的锂衍生物在甲苯溶液中反应制备的。令人惊讶的是，[NacnacTiCl·THF]与RP-P(SiMe)Li在四氢呋喃溶液中的反应通过涉及氮烯NAr从Nacnac骨架迁移到钛中心的自动氧化还原路径，生成了含磷膦亚胺配体的钛配合物[NacnacTi(Cl)(η-P-PtBu)]。通过单晶X射线衍射确定了[NacnacTi(Cl){η-P(SiMe)-PtBu}]（1a）和[NacnacTi(Cl)(η-P-PtBu)]（两种异构体2a1、2a2）以及[NacnacTi(Cl){η-P(SiMe)-PiPr}]（1b）和[NacnacTi(Cl)(η-P-PiPr)]（2b）的固态结构，这些结构清楚地显示了固态下(MeSi)P-PR和P-PR部分的侧基几何构型。磷膦亚胺配合物[NacnacTi(Cl)(η-P-PR)]表明，膦亚胺磷原子的P NMR共振在溶液和固态中都出现在非常低的场强处。
