Stafford, Hannah and Rookes, Thomas M. and Wildman, Elizabeth P. and Balazs, Gabor and Wooles, Ashley J. and Scheer, Manfred and Liddle, Stephen T. (2017) Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV). ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56 (26). pp. 7669-7673. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | COORDINATE PHOSPHORUS ATOMS; BOND-FORMING REACTIONS; CARBENE-LIKE CHEMISTRY; P MULTIPLE BOND; TRIAMIDOAMINE COMPLEXES; TUNGSTEN COMPLEXES; TITANIUM COMPLEXES; OXO COMPLEX; U-IV=C; REACTIVITY; agostic-type interactions; phosphanides; phosphinidenes; X-ray crystallography; zirconium |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Dec 2018 13:10 |
| Last Modified: | 11 Feb 2019 13:17 |
| URI: | https://pred.uni-regensburg.de/id/eprint/688 |
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