Synthesis, structure, and mechanism of the isomers of ruthenium complexes based on HC≡CC(OH)(CH3)2 and ortho-Carborane dithiolate ligands

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Treatment of 16-electron complex ( p -cymene)Ru(S 2 C 2 B 10 H 10 ) ( 1 ) with HC≡CC(OH)(CH 3 ) 2 in chloroform at −10 °C leads to two isomers ( p -cymene)Ru(S 2 C 2 B 10 H 9 )(CH 2 CC(OH)(CH 3 ) 2 ) ( 2 and 3 ), which are converted to the corresponding complexes ( p -cymene)Ru(S 2 C 2 B 10 H 9 )(CH 2 CC(CH 3 )CH 2 ) ( 4 and 5 ) by loss of a water molecule at 62 °C, respectively. These complexes were characterized by elemental analysis, mass, IR and NMR spectroscopy. X-ray structural analysis were performed on 4 and 5 . The formation mechanisms for the title complexes were also studied. • ● In chloroform, treatment of 16e complex ( p -cymene)Ru(S 2 C 2 B 10 H 10 ) with HC≡CC(OH)(CH 3 ) 2 at − 10 °C leads to two isomers ( p -cymene)Ru(S 2 C 2 B 10 H 9 )(CH 2 CC(OH)(CH 3 ) 2 ), which are converted to the corresponding complexes ( p -cymene)Ru(S 2 C 2 B 10 H 9 )(CH 2 CC(CH 3 )CH 2 ) by loss of a water molecule at 62 °C, respectively. • ● Both isomers ( p -cymene)Ru(S 2 C 2 B 10 H 9 )(CH 2 CC(CH 3 )CH 2 ) have been characterized by IR, NMR, MS, elemental analysis and single-crystal X-ray diffraction. • ● The formation mechanisms for the title complexes were studied. Treatment of 16-electron complex ( p -cymene)Ru(S 2 C 2 B 10 H 10 ) ( 1 ) with HC≡CC(OH)(CH 3 ) 2 in chloroform at − 10 °C leads to two isomers ( p -cymene)Ru(S 2 C 2 B 10 H 9 )(CH 2 CC(OH)(CH 3 ) 2 ) ( 2 and 3 ), which are converted readily to the corresponding complexes ( p -cymene)Ru(S 2 C 2 B 10 H 9 )(CH 2 CC(CH 3 )CH 2 ) ( 4 and 5 ) by loss of a water molecule at 62 °C. These complexes were characterized by elemental analysis, mass, IR and NMR spectroscopy. X-ray structural analysis were performed on 4 and 5 . The formation mechanisms for the title complexes were also studied. The complex 4 crystallizes in monoclinic system, space group P 2 1 /n with a = 11.082(2), b = 14.529(3), c = 15.230(3) Å , α = 90, β = 101.022(2), γ = 90°, C 17 H 30 B 10 RuS 2 , Mr = 507.70, V = 2407.1(9) Å 3 , Dc = 1.401 g/cm 3 , Z = 4, F (0 0 0) = 1032, µ (Mo Kα ) = 0.828 mm −1 , R = 0.0424 and ωR = 0.1089 for 4470 observed reflections ( I > 2 σ ( I )). The complex 5 crystallizes in monoclinic system, space group P 2 1 /c with a = 16.0543(16), b = 10.5758(11), c = 14.0954(14) Å , α = 90, β = 99.0430(10), γ = 90°, C 17 H 30 B 10 RuS 2 , Mr = 507.70, V = 2363.5(4) Å 3 , Dc = 1.427 g/cm 3 , Z = 4, F (0 0 0) = 1032, µ (Mo Kα ) = 0.844 mm −1 , R = 0.0444 and ωR = 0.1076 for 3745 observed reflections ( I > 2 σ ( I )).