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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 international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201707921
Subject(s) - phosphide , electron paramagnetic resonance , chemistry , molybdenum , crystallography , electron , transition metal , valence electron , chemical bond , electron transfer , natural bond orbital , photochemistry , metal , inorganic chemistry , density functional theory , nuclear magnetic resonance , computational chemistry , catalysis , physics , organic chemistry , quantum mechanics
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.