Abstract
Treatment of hexane-2,5-dione bis(thiosemicarbazones) ([CH3‒C{= N‒NH‒C(=S)‒NHR}‒CH2]2, R = H, L1H2; CH3, L2H2‒Me; CH2CH3, L3H2‒Et; C6H5, L4H2‒Ph) with nickel(II) acetate hydrate in refluxing ethanol gave a series of NiIIN2S2 metalloligands [Ni(L-R)] for the generation of hetero-bimetallic complexes. The reaction of equal mole each of [Ni(L1)], [Ni(L2‒Me)], [Ni(L3‒Et)], or [Ni(L4‒Ph)] with [RuCl2(dmso)4] (dmso = dimethyl sulfoxide) at reflux resulted in isolation of neutral dinuclear ruthenium-nickel complexes [RuCl2{(Ni(L1)}(dmso)2] (1), [RuCl2{(Ni(L2‒Me)}(dmso)2] (2), [RuCl2{(Ni(L3‒Et)}(dmso)2] (3), and [RuCl2{(Ni(L4‒Ph)}(dmso)2] (4). Interaction of [Ni(L-R)] with [CpRu(PPh3)2Cl] (Cp‒ = cyclopentadienyl) at room temperature led to formation of cationic dinuclear organoruthenium-nickel complexes [CpRu{(Ni(L1)}(PPh3)]Cl (5), [CpRu{(Ni(L2‒Me)}(PPh3)]Cl (6), [CpRu{(Ni(L3‒Et}(PPh3)]Cl (7), and [CpRu{(Ni(L4‒Ph}(PPh3)]Cl (8). New bimetallic ruthenium-nickel complexes 1–8 have been characterized spectroscopically, of which molecular structures of three complexes [RuCl2{(Ni(L2‒Me)}(dmso)2]·CH2Cl2 (2·CH2Cl2), [CpRu{(Ni(L2‒Me)}(PPh3)]Cl⋅EtOH (6⋅EtOH), and [CpRu{(Ni(L3‒Et}(PPh3)]Cl (7⋅H2O) have been established by single-crystal X-ray crystallography. Their catalytic activities for the acetalation of benzaldehyde in the presence of molecular H2 have been also investigated in this paper.
Published Version
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