Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry

A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

“…Concerned with undesired reactivity of the bound azide, complex 2 was treated with Me 3 SiOTf (OTf = trifluoromethanesulfonate) to enact ligand exchange.A ddition of two equiv of the silyl triflate cleanly formed an ew species with as lightly downfield shifted 31 P{ 1 H} NMR resonance (36.42 ppm, C 6 D 6 )a nd am arginally downfield-shifted 15 N NMR signal (842.22 ppm). As olid-state structure of nitride triflate 3 was not obtained, but the similarity of the spectroscopic signature with that of precursor 2,t he loss of the N 3 À signals in the 15 NN MR spectrum, and as ingle 19 FNMR resonance at À76.91 ppm support its assignment.…”

“…4), which help destabilize the often unreactive M À Nb ond, are,t oo ur knowledge,u nknown for early transition metals.This motivated an investigation of the electronic structure of am onometallic model of 5 and its precursor, 3.T he bonding situation of square pyramidal precursor 3 is analogous to that of its Mo IV phosphide congener. [19] Thed -electrons occupy aM oo rbital of d xy parentage that is strictly non-bonding with respect to the nitride,p ermitting the formal MoNt riple bond. Upon two electron reduction, in this geometry,the d xz and/or d yz orbitals (MoN p*) would become occupied, lowering the formal MoÀNb ond order and likely making this complex unstable/ unisolable.…”

Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

“…We recently reported the first examples of transition metal complexes with both terminal phosphide ligands and d‐electrons ( 2 , Scheme ) . Herein, we extend this molecular Mo pnictogenide chemistry, reporting the preparation of a series of low‐valent μ‐phosphido complexes.…”

Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

“…[9] Herein, we extend this molecular Mo pnictogenide chemistry,r eporting the preparation of as eries of low-valent m-phosphido complexes.T hese compounds model important steps invoked in the proposed mechanism of heterogeneous HER and provide an experimental benchmark for the thermochemistry of ab ridging phosphinidene PÀHb ond. [9] Herein, we extend this molecular Mo pnictogenide chemistry,r eporting the preparation of as eries of low-valent m-phosphido complexes.T hese compounds model important steps invoked in the proposed mechanism of heterogeneous HER and provide an experimental benchmark for the thermochemistry of ab ridging phosphinidene PÀHb ond.…”

“…We recently reported the first examples of transition metal complexes with both terminal phosphide ligands and delectrons (2,S cheme 1). [9] Herein, we extend this molecular Mo pnictogenide chemistry,r eporting the preparation of as eries of low-valent m-phosphido complexes.T hese compounds model important steps invoked in the proposed mechanism of heterogeneous HER and provide an experimental benchmark for the thermochemistry of ab ridging phosphinidene PÀHb ond.…”