The reaction of RuCl2(PPh3)3 with HSiX3 in benzene produced (η6-benzene)Ru(PPh3)(SiX3)2
(SiX3 = SiCl3 (1), SiMeCl2 (2)) as white to light yellow solids in high yields (>80%). A mixture
of (η6-benzene)Ru(PPh3)(SiMe2Cl)2 (3), (η6-benzene)Ru(PPh3)(SiMe2Cl)(SiMeCl2) (4), and 2,
due to silicon substituent redistribution, was obtained from the reaction of RuCl2(PPh3)3
with HSiMe2Cl in benzene. (η6-benzene)Ru(PPh3)(SiMe3)2 (5) was prepared by the methylation of 1, 2, or the 3/4 mixture with AlMe3. The related complexes (η6-arene)Ru(PPh3)(SiMeCl2)2 (arene = toluene (6), o-xylene (7), m-xylene (8), p-xylene (9), mesitylene (10),
anisole (11)) were obtained from the reaction of RuCl2(PPh3)3 with HSiMeCl2 in the
corresponding arene solvent at elevated temperature. Complexes 1, 2, and 5 were structurally
characterized by single-crystal X-ray diffraction and exhibit a characteristic three-legged
“piano-stool” geometry. The Ru−Si distances, in these complexes, ranged from 2.322 to 2.438
Å; the Ru−Si distance increased as the number of methyl groups on silicon increased.
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