Substituent-Free Gallium by Hydrogenolysis of Coordinated GaCp~*: Synthesis and Structure of Highly Fluxional [Ru2(Ga)(GaCp~*)7(H)3]

摘要

Monovalent organo Group 13 metal compounds ER (E = Al, Ga, In; R = bulky substituent: e.g. alkyl, aryl, C5Me5 (Cp~*), amides, β-diketiminate, amidinates, guanidinates) behave as very potent o-donor ligands in coordination chemistry. A more recent highlight is [η~5-{(Me3Si)C5H4}3U(AlCp~*)] containing the first unsupported actinide-aluminum bond. Much work has been done elucidating the bonding properties of similar d/f-block compounds of the general formula [L_aM_b(ER)_c] . But far less information has been gathered on the reaction chemistry and associated potential applications of this class of compounds. The homoleptic compounds [M_a(ECp~*)4] are particularly interesting because of the flexible binding properties of the Cp~* at the Group 13 metal atom. The soft chemical synthesis of M/E Hume-Rothery phases using all-hydrocarbon ligand [ML_n] and ECp_n~* as precursors (n = 1, E = Al, Ga; n = 2, E = Zn; M = Cu, Ni) and the recent discovery of [Mo(ZnMe)9(ZnCp~*)3] and [{Mo(CO)4}4(Zn)6(μ-ZnCp~*)4] , resulting from the reactions of [Mo(GaCp~*)_n(CO)_(6-n)] with ZnMe2, illustrate novel prospects for a targeted approach to intermetallic nanomaterials based on molecular Group 13/transition-metal complexes.