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The effect of replacing carbonyl with acetonitrile on the reactivity of the bimetallic system [Mo2Cp2(μ-SMe)3(L)2]+ (L=CO, CH3CN). Crystal structure of [Mo2Cp2(μ-SMe)2(CH3CN) 4](BF4)2

Abstract : [Mo2Cp2(μ-SMe)3(CH3CN) 2](BF4) (1) reacts with H[BF4] in acetonitrile at room temperature to give the tetrakis (acetonitrile) compound [Mo2Cp2(μ-SMe)2(CH3CN) 4](BF4)2 (3) through replacement of one SMe bridge by two terminal CH3CN ligands. In sharp contrast, the carbonyl analogue [Mo2Cp2(μ-SMe)3(CO)2]+ (2) fails to undergo a similar reaction. This suggests that the electronic properties of the ancillary ligands L in the [Mo2Cp2(μ-SMe)3L2]+ moiety govern the activation of a sulfur atom in protonation reactions. An X-ray diffraction study shows that 3 contains two CpMo(CH3CN)2 units bridged by two SMe groups and linked by a long Mo-Mo bond of 3.000(1) Å.
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Submitted on : Thursday, April 19, 2018 - 2:49:45 PM
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Philippe Schollhammer, François Pétillon, J. Talarmin, K.W. Muir. The effect of replacing carbonyl with acetonitrile on the reactivity of the bimetallic system [Mo2Cp2(μ-SMe)3(L)2]+ (L=CO, CH3CN). Crystal structure of [Mo2Cp2(μ-SMe)2(CH3CN) 4](BF4)2. Inorganica Chimica Acta, Elsevier, 1999, 284, pp.107--111. ⟨10.1016/S0020-1693(98)00266-7⟩. ⟨hal-01771400⟩

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