Complexes [Ru(η5-C5H5){κ3(P,C,C)-Ph2P(CH2)
n
CHCH2}(MeCN)][PF6] (n = 1 (1), 2 (2)) react with
C⋮C bonds of propargylic alcohols to yield regioselectively the complexes [Ru(η5-C5H5){κ(P),η4-Ph2P(CH2)
n
CHCHC(R)CH2}][PF6] (n = 1, R = CPh2OH (3), C(C12H8)OH (4), C(C4H8)OH (5), CMePhOH
(6a, 6b); n = 2, R = CPh2OH (7), C(C4H8)OH (8), CMePhOH (9a, 9b), CHPhOH (10a, 10b)). The
reaction of complex 1 with terminal alkynes also leads regioselectively to the complexes [Ru(η5-C5H5){κ(P),η4-(2Z,4E)-Ph2PCH2CHCHCHCH(R)}][PF6] (R = Ph (11), p-MeC6H4 (12)). Single-crystal X-ray
diffraction analyses for complexes 9a, 9b, 10b, and 12 have been carried out and allow the unambiguous
assignment of the stereochemistry of the complexes. DFT calculations regarding the thermodynamic
stability of the obtained products have also been performed.