Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV).

ABSTRACT: The reaction of [Zr(Tren^DMBS )(Cl)] [Zr1; Tren^DMBS =N(CH₂ CH₂ NSiMe₂ Bu^t )₃ ] with NaPH₂ gave the terminal parent phosphanide complex [Zr(Tren^DMBS )(PH₂ )] [Zr2; Zr-P=2.690(2)?Å]. Treatment of Zr2 with one equivalent of KCH₂ C₆ H₅ 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(Tren^DMBS )(PH)][K(B15C5)₂ ] [Zr3; Zr=P=2.472(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 is similarly polarized, and thus as covalent, as essentially isostructural U=P and Th=P analogues.

SUBMITTER: Stafford H 

PROVIDER: S-EPMC5575506 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature