Heterometallic uranium/molybdenum nitride synthesis via partial N-atom transfer

Abstract

The reaction of a terminal Mo(II) nitride with a U(III) complex yields an heterodimetallic U-Mo nitride which is the first example of a transition metal-capped uranium nitride. The nitride is...

Cation assisted binding and cleavage of dinitrogen by uranium complexes

“…The few multimetallic uranium–alkali ion systems reported so far that effect the four-electron reduction of N 2 , 1 j , m ,3 h or even its complete cleavage to nitride, 4 all contain the potassium cation. It should be noted that although the number of reported uranium nitride complexes is rapidly increasing 12,13 only three examples of uranium nitrides have been obtained from N 2 reduction (Chart 1).…”

Progress in the chemistry of molecular actinide-nitride compounds

“…In 2022, Mazzanti, Agapie, and co-workers reported the first example of a heterometallic uranium-transition metal nitride complex, [Na(U(OSi(O t Bu) 3 (μ-N)(MoP 2 ))] (70) (P 2 = terphenyl diphosphine ligand), generated from partial N-transfer to the U( iii ) precursor, [U III (OSi(O t Bu) 3 ) 3 (THF) 2 ], from the Na-capped molybdenum( ii ) nitride, [Na(N)Mo II P 2 ] (70a) ( Scheme 14a ). 117 The solid-state molecular structure of 70 displays a U–Mo heterometallic complex bridged by a N 3− ligand, where the U and Mo centers are in close proximity with a U–Mo distance of 3.1032(2), which was slightly shorter than the distances found in other heterometallic U–Mo complexes bridged by phosphinoamide ligands (3.1682(4), 3.159(2) Å). 118 The short U–Mo bond distance highlights the ability of the bridging nitride and bridging arene of the P 2 ligand in 70 to promote metal–metal interactions.…”

“…resulted in the reductive carbonylation of the nitride, leading to the formation of NaN13CO (10–50% yield) and the previously reported Mo(0) carbonyl complexes, [P 2 Mo 0 ( 13 CO)] or [P 2 Mo 0 ( 13 CO) 3 ] (in low yield), as well as multiple unidentified diamagnetic species ( Scheme 16b ). 117 The uranium species formed in the reaction could not be identified, but the formation of NaN 13 CO was unambiguously demonstrated by 13 C NMR spectroscopy of the reaction mixture in D 2 O. The reductive carbonylation of the U( v ) nitride most likely proceeds with release of the Mo(0) complex, but reactivity with complex 70 was not ruled out.…”

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

“…This work provides a useful strategy for promoting productive group transfer reactivity in stable early transition-metal nitrides. Recently, Mazzanti, Maron, and Agapie showed that the nitride ligand in Na[ 1008 ] is partially transferred to the uranium(III) precursor [U(OSi t Bu 3 ) 3 ­(thf) 2 ] ( 1012 ), affording the first example of a transition metal-capped uranium nitride Na[U(OSi t Bu 3 ) 3 ­(μ-N)Mo(tpdp)] ( 1013 ) . The experimental and computational data point to an N -transfer accompanied by a two-electron transfer from uranium to molybdenum, formally resulting in the nitride triply bonded to U(V) and singly bonded to Mo(0).…”