Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 46, Pages 14502-14506Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201707921
Keywords
group transfer; molybdenum; phosphide coupling; pulse EPR; terminal phosphides
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Funding
- Sloan fellowship
- NSF
- NSF [CHE-1151918, NSF-1531940]
- Caltech
- Cottrell fellowship
- Dreyfus fellowship
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1151918] Funding Source: National Science Foundation
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A terminal Mo phosphide was prepared through the group transfer of both P and Cl atoms from chloro-substituted dibenzo-7 lambda(3)-phosphanorbornadiene. This compound represents the first structurally characterized terminal transitionmetal phosphide with valence d electrons. In the tetragonal ligand field, these electrons populate an orbital of d(xy) parentage, an electronic configuration that accommodates both metal d electrons and a formal M P triple bond. Single-electron oxidation affords a transient open-shell terminal phosphide cation with significant spin density on P, as corroborated by continuous wave (CW) and pulse electron paramagnetic resonance (EPR) characterization. Facile P-P bond formation occurs from this species through intermolecular phosphide coupling.
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