Synthesis and characterization of cyclopentadienyl sulfur niobium complexes

A trimetallic sulfide cluster [Nb-3(eta(5)-C5Me5)(3)Cl-3(mu(3)-Cl)(mu-S)(3)(mu(3)-S)] (2) has been synthesized from the reaction of [Nb(eta(5)-C5Me5)Cl-4] (1) with (Me3Si)(2)S in a 4:3 ratio by the release of SiClMe3. The trinuclear nature of complex 2 has been established by single crystal X-ray diffraction analysis. Thermal treatment of 2 with SiH3Ph generated the dinuclear niobium(IV) complex [Nb-2(eta(5)-C5Me5)(2)Cl-2(mu-S)(2)] (3) in a quantitative way. Likewise, one-pot syntheses of 3 has been developed from reaction of 1, (Me3Si)(2)S, and SiH3Ph in toluene. A series of dinuclear sulfide niobium(IV) derivatives [Nb-2(eta(5)-C5Me5)(2)R-2(mu-S)(2)] (R = Me 4, Et 5, CH2SiMe3 6, C3H5 7, CH2Ph 8, nBu 9) can easily be obtained from the reaction of 3 with 2 equiv of the corresponding alkylating reagents. Single crystal X-ray diffraction analyses of 6 and 7 showed in all cases a trans disposition of the substituents. (c) 2019 Elsevier B.V. All rights reserved.