Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)

Research output: Contribution to journalArticle

  • External authors:
  • Hannah Stafford
  • Thomas Rookes
  • Elizabeth Wildman
  • Gabor Balazs
  • Ashley J Wooles
  • Manfred Scheer

Abstract

The reaction of [Zr(TrenDMBS)(Cl)] [Zr1, TrenDMBS =
N(CH2CH2NSiMe2But)3] with NaPH2 gave the terminal parent phosphanide
complex [Zr(TrenDMBS)(PH2)] [Zr2, Zr-P = 2.685(2) Å]. Treatment of Zr2
with one equivalent of KCH2C6H5 and two equivalents of benzo-15-crown-5
ether (B15C5) afforded an unprecedented example outside of matrix
isolation of a structurally authenticated transition metal terminal parent
phosphinidene complex [Zr(TrenDMBS)(PH)][K(B15C5)2] [Zr3, Zr=P =
2.469(2) Å]. DFT calculations reveal a polarized-covalent Zr=P double
bond, with a Mayer bond order of 1.48, and together with IR spectroscopic
data also suggest an agostic-type Zr···HP interaction [∠ZrPH = 66.7°] which
is unexpectedly similar to that found in cryogenic spectroscopically
observed phosphinidene species. Surprisingly, computational data suggest
that the Zr=P linkage reported here is as polarized, and thus as covalent,
as essentially isostructural U=P and Th=P analogues.

Bibliographical metadata

Original languageEnglish
JournalAngewandte Chemie - International Edition
Volume56
Issue number26
Early online date26 May 2017
DOIs
Publication statusPublished - 2017

Related information