Heterobimetallic drive and cooperativity lead to a striking scenario for C-H bond activation and heteroaggregation involving Mo-III dimers. Reaction of (RO)(3)Mo Mo(OR)(3) with molar excess of ZnMe2 at -78 degrees C affords the novel mixed Zn, Mo oxo clusters [Mo-2(MeZn)(6)(mu(2)-Me)(mu(3)-CH2)(2)(OR)(7)] 1 (R = neopentyl) and 2 (R = cyclohexyl) preserving the Mo Mo triple bond, while the same reaction performed at ambient temperature gives rise to the related cluster [Mo-2(MeZn)(6)(mu(2)-CH2)(mu(3)-CH2)(2)(OR)(6)] 3. These complexes represent the first examples of heterobimetallic Mo Mo complexes with bridging methyl and methylene groups and agostic C-H -> Mo interactions, as well as penta-coordinate carbon. The complexes 1-3 were characterized by elemental analyses, multinuclear NMR and single-crystal X-ray diffraction analysis.
Heterobimetallic drive and cooperativity lead to a striking scenario for C–H bond activation and heteroaggregation involving MoIII dimers. Reaction of (RO)3Mo![[triple bond, length as m-dash]](http://www.rsc.org/images/entities/char_e002.gif)
Mo(OR)3 with molar excess ofZnMe2 at–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 MoMocomplexes with bridging methyl and methylene groups and agostic C–H→Mo interactions, as well as penta-coordinate carbon. The complexes 1–3 were characterized by elemental analyses, multinuclear NMR and single-crystal X-ray diffraction analysis.
![Graphical abstract: Activation of C–H bonds mediated by Mo [[triple bond, length as m-dash]] Mo moieties in heterobimetallic Zn/O/Mo clusters](http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=B917585G "Graphical abstract")