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Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry
Author(s) -
Buss Joshua A.,
Oyala Paul H.,
Agapie Theodor
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201707921
Subject(s) - phosphide , electron paramagnetic resonance , chemistry , molybdenum , crystallography , electron , transition metal , valence electron , chemical bond , delocalized electron , electronic structure , metal , inorganic chemistry , nuclear magnetic resonance , computational chemistry , physics , biochemistry , organic chemistry , quantum mechanics , catalysis
A terminal Mo phosphide was prepared through the group transfer of both P and Cl atoms from chloro‐substituted dibenzo‐7λ 3 ‐phosphanorbornadiene. This compound represents the first structurally characterized terminal transition‐metal 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.