Abstract
The processes of formation of antiferromagnetic heterometallic trinuclear clusters Cp2Cr2(μ-SCMe3)2(μ3-S)2MLn (MLn = Re(CO)(NO), W(NO)2, W(NO)Cl, and W(NO)(SCMe3)) from the antiferromagnetic binuclear chromium(iii) complex Cp2Cr2(μ-SCMe3)2(μ-S) (1) and nitrosyl-containing halide derivatives of ReI and W0 were considered. It is shown that adducts of1 with MLm (MLm = Re(NO)(CO)2Cl2, W(NO)2C12·1, and W2(NO)2(CO)4I2) are formed at the first stage. Then they loose the CpCrHal2 moiety and transform into the reactive remetalation products, CpCr((μ-SCMe3)2(μ-S)MLx (M = Re and W). The latter complexes join the electron-deficient CpCrS moiety to generate triangular clusters. The magnetic behavior of antiferromagnetic adducts and triangular clusters is discussed, and the existence of correlations between the energy of spin-spin exchange (−2J(Cr-Cr)) and Cr-Cr and Cr-S(sulfide) bond lengths is mentioned.
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