Non-oxido divanadium(IV) and divanadium(V) thiolate complexes with a new type of chalcogenide bridging motif

作者：Wu Hong Ming; Chang Ya Ho; Tsai Yi Fang; Hsu Kuei Fang; Lee Gene Hsiang; Hsu Hua Fen^*

来源：Dalton Transactions, 2015, 44(10): 4468-4473.

DOI：10.1039/c4dt03934c

In our effort to study vanadium chalcogenide chemistry, we have synthesized and characterized a class of non-oxido divanadium(IV) and divanadium(V) complexes with chalcogenide and dichalcogenide as bridges. All structures consist of a similar divanadium motif, in which two metal centers are bridged by one mu-chalcogenide and one mu-eta(2):eta(2)-dichalcogenide, forming a V-2(mu-E)(mu-eta(2):eta(2)-E-2) (E = S or Se) core structure. These compounds are [V-2(IV)(PS3)(2)(mu-Se-2)(mu-Se)][PPh4](2) (1), [V-2(V)(PS3'')(2)(mu-Se-2)(mu-Se)] (2), [V-2(V)(PS3'')(2)(mu-S-2)(mu-S)] (3a) and [V-2(V)(PS3)(2)(mu-S-2)(mu-S)] (3b) ([PS3](3-) = P(C6H4-2-S)(3) and [PS3''](3-) = P(C(6)H(3-)3-SiMe3-2-S)(3)). Compound 1 exhibits diamagnetic behavior, indicating strong antiferromagnetic coupling between two d(1) centers. Compounds 2 and 3a-b have the highest oxidation states for vanadium ions (+5/+5) among those reported divanadium chalcogenide clusters. The work demonstrates that highvalent divanadium chalcogenide clusters can be obtained with the activation of elemental chalcogens by low-valent vanadium ions.

• 出版日期2015