Abstract
The reaction of [Zr(Tren(DMBS))(Cl)] [Zr1; Tren(DMBS) = N(CH2CH2NSiMe2But)(3)] with NaPH2 gave the terminal parent phosphanide complex [Zr(Tren(DMBS))(PH2)] [Zr2; Zr P = 2.690(2) angstrom]. 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 ...
Abstract
The reaction of [Zr(Tren(DMBS))(Cl)] [Zr1; Tren(DMBS) = N(CH2CH2NSiMe2But)(3)] with NaPH2 gave the terminal parent phosphanide complex [Zr(Tren(DMBS))(PH2)] [Zr2; Zr P = 2.690(2) angstrom]. 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(Tren(DMBS))(PH2)][K(B15C5)(2)] [Zr3; Zr=P=2.472(2) angstrom]. DFT calculations reveal a polarized-covalent Zr center dot center dot center dot HP double bond, with a Mayer bond order of 1.48, and together with IR spectroscopic data also suggest an agostic-type Zr center dot center dot center dot HP interaction [(sic)(ZrPH) = 66.7 degrees] 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.
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