In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2013, No. 22-23 ( 2013-08-06), p. 3916-3929
Abstract:
The transformation of vanadium(III) azides, [(nacnac)V(N 3 )(X)] n {nacnac = [ArNC(CH 3 )] 2 CH – , Ar = 2,6‐(CHMe 2 ) 2 C 6 H 3 ; X = Ntol 2 – , where tol = 4‐MeC 6 H 4 , n = 1; X = ArO – , n = 2}, to their corresponding vanadium(V) nitrides, [(nacnac)V≡N(X)], was investigated through an isotopic labeling crossover experiment. The nuclearity of the azide species is dependent on the size of the supporting ligand, X, with X = ArO – , thus featuring a V 2 N 6 core with two μ 2 ‐1,3‐N 3 bridging ligands across the V III centers. SQUID magnetization studies and multifrequency, high‐field EPR (HFEPR) experiments reveal the mononuclear azide complex to be consistent with an S = 1 system, while the dimeric azide system is weakly antiferromagnetically coupled with a spin singlet ground state and thermally accessible triplet and quintet states. These combined results suggest that the transformation of a vanadium(III) azide to a vanadium(V) nitride most likely occurs by a bimetallic mechanism, where Lewis bases inhibit N 2 extrusion. Room‐temperature generation of the nitride products from their corresponding azides can also be accomplished stoichiometrically with a Lewis acid, such as B(C 6 F 5 ) 3 , and catalytically, through an unsaturated vanadium(II) fragment, [(nacnac)V(Ntol 2 )].
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2013.22/23
DOI:
10.1002/ejic.201300178
Language:
English
Publisher:
Wiley
Publication Date:
2013
detail.hit.zdb_id:
1475009-0
