Activation of C–H bonds mediated by MoMo moieties in heterobimetallic Zn/O/Mo clustersElectronic supplementary information (ESI) available: Additional experimental details. CCDC reference numbers 714288, 714289and 714290. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b917585g

Heterobimetallic drive and cooperativity lead to a striking scenario for C–H bond activation and heteroaggregation involving MoIIIdimers. Reaction of (RO)3MoMo(OR)3with molar excess of ZnMe2at–78 °C affords the novel mixed Zn, Mo oxo clusters [Mo2(MeZn)6(μ2-Me)(μ3-CH2)2(OR)7] 1(R = neopentyl) and 2(R = cyclohexyl) preserving the MoMo triple bond, while the same reaction performed at ambient temperature gives rise to the related cluster [Mo2(MeZn)6(μ2-CH2)(μ3-CH2)2(OR)6] 3. These complexes represent the first examples of heterobimetallic MoMo complexes with bridging methyl and methylene groups and agostic C–H→Mo interactions, as well as penta-coordinate carbon. The complexes 1–3were characterized by elemental analyses, multinuclear NMR and single-crystal X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]