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In search for new bonding modes of the methylenedithiolato ligand: novel tri- and tetra-metallic clusters

Abstract : Building upon our earlier results on the chemistry of diruthenium analogue of pentaborane (9) with heterocumulenes, we continued to investigate the reactivity of arachno-[(Cp*Ru)2(B3H8)(CS2H)], 1, (Cp* = η5-C5Me5) towards group 7 and 8 transition metal carbonyl compounds under photolytic and thermolytic conditions. The metal carbonyl compounds show diverse reactivity pattern with arachno-1. For example, the photolysis of arachno-1 with [Re2(CO)10] yielded [(Cp*Ru)2B3H5(CH2S2)\Re(CO)4\2], 2, [(Cp*RuCO)2(μ-H)2(CH2S2)\Re(CO)4\\Re(CO)3\], 3 and [(Cp*Ru)2(μ-CO)(μ-H)(CH2S2)\Re(CO)3\], 4. The geometry of 2 with a nearly planar eight-membered ring containing heavier transition metals rhenium, ruthenium is unprecedented. Compounds 3 and 4 can be considered as M4-quadrilateral and M3-triangle with a methylenedithiolato ligand attached to the metal centres, respectively. [Mn2(CO)10], on the other hand, reacts with arachno-1 to yield heterometallic binuclear [(Cp*RuCO)\Mn(CO)4\(μ-H)(SCH3)], 5 and homocubane [(Cp*Ru)2\Mn(CO)3\-(CS2H2)B3H4], 6. In an attempt to generate group 8 analogues of 2–5, we performed the reaction of arachno-1 with [Fe2(CO)9] and [Ru3(CO)12]. Although, the objective of isolating analogous compounds was not achieved, the reaction with [Fe2(CO)9] led to novel tetrahedral cluster [(Cp*RuCO)\(Fe(CO)3\2S(μ-H)], 7. [Ru3(CO)12], in contrast, yielded known compounds [\Cp*Ru(CO)\2B2H6], 9 and [Cp*Ru(CO)2]2, 10. All the cluster compounds have been characterized by mass spectrometry, IR, and 1H, 11B, and 13C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis of 2–5 and 7
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Submitted on : Friday, July 10, 2015 - 10:40:09 AM
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R. S. Anju, Koushik Saha, Bijan Mondal, Thierry Roisnel, Jean-François Halet, et al.. In search for new bonding modes of the methylenedithiolato ligand: novel tri- and tetra-metallic clusters. Dalton Transactions, Royal Society of Chemistry, 2015, 44 (25), pp.11306--11313. ⟨10.1039/C5DT00179J⟩. ⟨hal-01174901⟩



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