Reaction of Ru(η 4 -C 8 H 12 )(η 6 -C 8 H 10 ) (1) or Ru(η 4 -C 8 H 11 ) 2 (2) with tertiary phosphines gives Ru(η 4 -C 8 H 10 )L 3 [L ) PMe 3 (4a), PMe 2 Ph (4b), PEt 3 (4c), PEt 2 Ph (4d), P(n-Bu) 3 (4e)]. The cyclooctatriene moiety in 4a oxidatively adds to the ruthenium, giving Ru(6-η 1 :1-3-η 3 -C 8 H 10 )-L 3 [L ) PMe 3 (3a), PMe 2 Ph (3b)]. Complexes 4c-e dissociate one phosphine ligand in solution, affording the (hydrido)ruthenium complexes RuH(η 5 -C 8 H 9 )L 2 [L ) PEt 3 (5c), PEt 2 -Ph (5d), P(n-Bu) 3 (5e)]. Whereas prolonged heating of 4c at 70 °C caused disproportionation of the η 4 -C 8 H 10 moiety giving a mixture of the cyclooctatetraene complex Ru(η 4 -C 8 H 8 )(PEt 3 ) 3 (6) and RuH(η 5 -C 8 H 11 )(PEt 3 ) 2 ( 7), heating of 1 with PEt 3 , 4c, or 4d in the presence of 1,5-C 8 H 12 at 70 °C gave Ru(η 4 -bicyclo[4.The molecular structures of 3b, 4c, 6, and 8b have been established by X-ray structure analysis.

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