Reaction of RuCl 2 (PPh 3 ) 3 with bis(dicyclohexyl)-1,4-phosphinobutane (dcypb) under N 2 affords access to a formerly elusive family of dcypb complexes based on the RuCl 2 (PP) core. Under Ar or vacuum atmosphere, decomposition occurs via Ru-promoted dehydrogenation of the dcypb ligand. While the N 2 -stabilized species [RuCl 2 (dcypb)] 2 (N 2 ) (4a) is easily handled under N 2 in nonchlorinated solvents, reaction with chlorinated solvents rapidly yields paramagnetic Ru 2 Cl 5 (dcypb) 2 (5). The N 2 ligand within 4a is readily displaced under H 2 or CO atmosphere, yielding Ru 2 Cl 4 (dcypb) 2 (H 2 ) (6) or RuCl 2 (dcypb)(CO) 2 , the latter as a mixture of ccc-(7) and tcc-(8) isomers. Benzylidene derivative RuCl 2 (dcypb)(CHPh) (1a), prepared in situ by reaction of 4a with PhCHN 2 , proves exceptionally active in ring-opening metathesis polymerization (ROMP) of norbornene. The X-ray crystal structure of 5 is reported: triclinic, a = 13.390(2), b = 15.726(2), c = 19.524(2) Å, α = 77.325(2), β = 70.964(2), γ = 73.478(2)°, with space group P[Formula: see text] and Z = 2.
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Amoroso et al. (2001) studied this question.