Photoinduced rearrangements of ring-coupled bis(cyclopentadienylrutheniumdicarbonyl) compounds of the form Ru-2(CO)(4)(eta(5),eta(5)-C(5)H(4)LC(5)H(4)) (L=CH2-, (CH3)(2)C-, C2H4- and (CH3)(2)Si-) - The molecular structure of [Ru(CO)(2)][Ru(CO)(2)Cl](eta(5),eta(5):eta(1)-C5H4CH2C5H3)

Compounds of the general form Ru-2(CO)(4)(eta(5),eta(5)-C(5)H(4)LC(5)H(4)), where L = CH2-, (CH3)(2)C-, C2H4- and (CH3)(2)Si-, have been found to undergo photolysis in deuterobenzene or deuterotoluene to give 'twisted' ruthenium hydride complexes of the form [Ru(CO)(2)][Ru(CO)(2)H](eta(5),eta(5):eta(1)-C(5)H(4)LC(5)H(3)). Reaction of these hydrides with chlorocarbons resulted in the formation of the corresponding chlorides which could be isolated and characterized by IR, H-1 and C-13 NMR, mass spectrometry, and elemental analysis. In the particular case of Ru-2(CO)(4)[eta(5),eta(5)-C5H4(CH3)(2)SiC5H4] a secondary photochemical reaction occurs with formation of [Ru(CO)(2)](2)(mu-eta(5):eta(1)-C5H4)[mu-(CH3)(2)Si-(eta(5)-C5H4)] in which Ru-Ru and Cp-Si bonds have been broken and new Ru-Cp and Ru-Si bonds formed. The molecular structure of [Ru(CO)(2)][RU(CO)(2)Cl](eta(5),eta(5):eta(1)-C5H4CH2C5H3) was determined by X-ray crystallography:monoclinic, Cc, a = 27.636(5) Angstrom, b = 9.058(2) Angstrom, c = 14.545(5) Angstrom, beta = 120.85(3)degrees, V = 3126(2) Angstrom(3), Z = 8, R(F)= 2.29%.