Activation of C-H bonds mediated by Mo Mo moieties in heterobimetallic Zn/O/Mo clusters


Ma J., AKSU Y., Gregoriades L. J., Sauer J., Driess M.

DALTON TRANSACTIONS, vol.39, no.1, pp.103-106, 2010 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 39 Issue: 1
  • Publication Date: 2010
  • Doi Number: 10.1039/b917585g
  • Journal Name: DALTON TRANSACTIONS
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.103-106
  • Akdeniz University Affiliated: No

Abstract

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]Mo(OR)3 with molar excess ofZnMe2 at–78 °C affords the novel mixed ZnMo oxo clusters [Mo2(MeZn)62-Me)(μ3-CH2)2(OR)7]1 (R = neopentyl) and 2 (R = cyclohexyl) preserving the Mo[triple bond, length as m-dash]Mo triple bond, while the same reaction performed at ambient temperature gives rise to the related cluster [Mo2(MeZn)62-CH2)(μ3-CH2)2(OR)63. These complexes represent the first examples of heterobimetallic Mo[triple bond, length as m-dash]Mocomplexes 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
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.