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Issue 7, 2011
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Terminal hafnium phosphinidene complexes and phosphinidene ligand exchange

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Abstract

Thermolysis of the structurally characterized hafnium phosphide complex, CpCp*HfMe(PHPh) (2), resulted in formation of the triphosphanato compound CpCp*Hf(P3Ph3) (3). Trapping reactions with PMe3 gave evidence for an intermediate phosphinidene complex, which was corroborated by synthesis of the related 2,6-dimesitylphenyl derivative CpCp*(Me3P)Hf[double bond, length as m-dash]P(dmp) (8). The hafnocene phenylphosphinidene intermediate can also be intercepted by a [2 + 2]-cycloaddition reaction with 2-butyne. However, reaction of 2 with either xylyl isocyanide or benzophenone gives insertion into the hafnium methyl bond. Under thermolytic conditions, metal dichloro complexes can efficiently intercept a phosphinidene fragment from 2 in a unique phosphinidene ligand exchange reaction. Thus, complex 2 reacts with (dippe)PtCl2 (11, dippe = 1,2-bis(diisopropylphosphino)ethane) and [N(Np)Ar]3TaCl2 (14, Np = neopentyl, Ar = 3,5-Me2C6H3) to afford phosphinidene complexes [(dippe)Pt(μ-PPh)]2 (12) and [N(Np)Ar]3Ta[double bond, length as m-dash]PPh (15), respectively, in good isolated yields. A derivative of 12, [(dippe)Pt]2(μ-PPh) (13), was structurally characterized.

Graphical abstract: Terminal hafnium phosphinidene complexes and phosphinidene ligand exchange

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Publication details

The article was received on 01 Mar 2011, accepted on 04 Apr 2011 and first published on 28 Apr 2011


Article type: Edge Article
DOI: 10.1039/C1SC00119A
Chem. Sci., 2011,2, 1320-1325

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    Terminal hafnium phosphinidene complexes and phosphinidene ligand exchange

    R. Waterman and T. D. Tilley, Chem. Sci., 2011, 2, 1320
    DOI: 10.1039/C1SC00119A

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