Photoinduced rearrangements of ring-coupled bis(cyclopentadienylrutheniumdicarbonyl) compounds of the form Ru 2(CO) 4( η5, η5-C 5H 4LC 5H 4) (L  CH n2-, (CH 3) 2C-, C 2H 4- and (CH 3) 2S-) The molecular structure of [Ru(CO) 2][Ru(CO) 2Cl]( η5, η5: η1-C 5H 4CH 2C 5H 3)

Abstract

Compounds of the general form Ru 2(CO) 4( η 5, η 5-C 5H 4LC 5H 4), where L  CH 2-, (CH 3) 2C-, C 2H 4- and (CH 3) 2Si-, have been found to undergo photolysis in deuterobenzene or deuterotoluene to give ‘twisted’ ruthenium hydride complexes of the form [Ru(CO) 2][Ru(CO) 2H]( η 5, η 5: η 1-C 5H 4LC 5H 3). Reaction of these hydrides with chlorocarbons in the formation of the corresponding chlorides which could be isolated and characterized by IR, 1H and 13C NMR, mass spectrometry, and elemental analysis. In the particular case of Ru 2(CO) 4[ η 5, η 5-C 5H 4(CH 3) 2SiC 5H 4] is secondary photochemical reaction occurs with formation of [Ru(CO) 2] 2( μ- η 5: η 1-C 5H 4)[ μ-(CH 3) 2Si-( η 5-C 5H 4)] in which in which RuRu and CpSi bonds have broken and new RuCp and RuSi bonds formed. The molecular structure of crystallography: monoclinic, Cc, a = 27.636(5) A ̊ , b = 9.058(2) A ̊ , c = 14.545(5) A ̊ , β = 120.85(3)°, V = 3126(2) A ̊ 3, Z = 8, R(F) = 2.29% .