Reactions of (Ph)tBuP-P(SiMe3)Li·3THF with [(PNP)TiCl2] and [MeNacNacTiCl2·THF]. Synthesis of first PNP titanium(IV) complex with phosphanylphosphinidene ligand [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] - Publication - Bridge of Knowledge

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Reactions of (Ph)tBuP-P(SiMe3)Li·3THF with [(PNP)TiCl2] and [MeNacNacTiCl2·THF]. Synthesis of first PNP titanium(IV) complex with phosphanylphosphinidene ligand [(PNP)Ti(Cl){η2-P-P(Ph)tBu}]

Abstract

Lithium derivative of diphosphane (Ph)tBuP-P(SiMe3)Li (1) was 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 phosphanylphosphido ligand [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2) was prepared in reaction of [MeNacNacTiCl2·THF] with (Ph)tBuP-P(SiMe3)Li in toluene solution with good yield and purity. Respective titanium(IV) complex involving phosphanylphosphinidene ligand [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) was synthesized by oxidation of complex (2) with [iBu3PAgCl]4. Interestingly, an analogus PNP titanium(IV) complex [(PNP)Ti(Cl){ɳ2-P-P(Ph)tBu}] (4) was obtained in the reaction of [(PNP)TiCl2] with (Ph)tBuP-P(SiMe3)Li in toluene solution and 1 : 1 molar ratio instead of the expected titanium(III) complex with phosphanylphosphido ligand. 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){ɳ2-P-P(Ph)tBu}] (4) determined by single-crystal X-ray diffraction reveald that in all obtained complexes both, the phosphanylphosphinidene (Ph)tBuP-P and phosphanylphosphido (Ph)tBuP-P(SiMe3) ligands are bidently coordinated to the metal center.

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Category:
Articles
Type:
artykuł w czasopiśmie wyróżnionym w JCR
Published in:
DALTON TRANSACTIONS no. 29, pages 1 - 11,
ISSN: 1477-9226
Language:
English
Publication year:
2018
Bibliographic description:
Ziółkowska A., Szynkiewicz N., Wiśniewska A., Pikies J., Ponikiewski Ł.: Reactions of (Ph)tBuP-P(SiMe3)Li·3THF with [(PNP)TiCl2] and [MeNacNacTiCl2·THF]. Synthesis of first PNP titanium(IV) complex with phosphanylphosphinidene ligand [(PNP)Ti(Cl){η2-P-P(Ph)tBu}]// DALTON TRANSACTIONS. -Vol. 29, (2018), s.1-11
DOI:
Digital Object Identifier (open in new tab) 10.1039/c8dt01833b
Verified by:
Gdańsk University of Technology

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