Gdansk University of Technology, Faculty of Chemistry, Department of Inorganic Chemistry, Gabriela Narutowicza Str. 11/12, 80-233 Gdansk, Poland.
Dalton Trans. 2018 Jul 24;47(29):9733-9741. doi: 10.1039/c8dt01833b.
Herein, the lithium derivative of diphosphane, (Ph)tBuP-P(SiMe3)Li (1), is isolated for the first time and investigated in reactions with β-diketiminate (MeNacnac- = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2C6H3) and PNP-pincer (PNP = N[2-PiPr2-4-methylphenyl]2) Ti(iii) complexes. The β-diketiminate titanium(iii) complex containing the phosphanylphosphido ligand [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2) is prepared via the reaction of [MeNacNacTiCl2·THF] with (Ph)tBuP-P(SiMe3)Li in toluene solution with good yield and purity. The corresponding titanium(iv) complex involving the phosphanylphosphinidene ligand [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) is synthesized via the oxidation of complex (2) with [iBu3PAgCl]4. Interestingly, an analogous PNP titanium(iv) complex, [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4), is obtained in the reaction of [(PNP)TiCl2] with (Ph)tBuP-P(SiMe3)Li in toluene solution and a 1 : 1 molar ratio instead of the expected titanium(iii) complex with the phosphanylphosphido ligand. The solid-state structures of (Ph)tBuP-P(SiMe3)Li·3THF (1), [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2), [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) and [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4) are determined by single-crystal X-ray diffraction, which reveals that in all obtained complexes, both the phosphanylphosphinidene (Ph)tBuP-P and phosphanylphosphido (Ph)tBuP-P(SiMe3) ligands are bidentate-coordinated to the metal center.
本文首次分离出二膦烷的锂衍生物(Ph)tBuP-P(SiMe3)Li（1），并研究了它与β-二酮亚胺（MeNacnac-= [Ar]NC(Me)CHC(Me)N[Ar]；Ar = 2,6-iPr2C6H3）和 PNP-钳形（PNP = N[2-PiPr2-4-methylphenyl]2）Ti(iii)配合物的反应。β-二酮亚胺钛(iii)配合物含有磷膦配体[MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}]（2），通过在甲苯溶液中用(Ph)tBuP-P(SiMe3)Li与[MeNacNacTiCl2·THF]反应制备，产率和纯度都很好。涉及磷膦亚磷酰基配体[MeNacNacTi(Cl){η2-P-P(Ph)tBu}]（3）的相应钛(iv)配合物通过用[ iBu3PAgCl]4氧化配合物（2）合成。有趣的是，在甲苯溶液中，用(Ph)tBuP-P(SiMe3)Li与[(PNP)TiCl2]反应得到了一个类似的 PNP 钛(iv)配合物[(PNP)Ti(Cl){η2-P-P(Ph)tBu}]（4），而不是预期的磷膦配体的钛(iii)配合物。(Ph)tBuP-P(SiMe3)Li·3THF（1）、[MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}]（2）、[MeNacNacTi(Cl){η2-P-P(Ph)tBu}]（3）和[(PNP)Ti(Cl){η2-P-P(Ph)tBu}]（4）的固态结构通过单晶 X 射线衍射确定，结果表明，在所得到的所有配合物中，磷膦亚磷酰基（Ph）tBuP-P 和磷膦配体（Ph）tBuP-P(SiMe3)都是双齿配位到金属中心。
