Abstract
The cyclopentadienyl-containing complex [Ru(η5-C5H5)(MeCN){κ3(P,C,C)-Ph2PCH2CH═CH2}][PF6] (1) reacts with allenes, giving regioselectively the η2-allene complexes [Ru(η5-C5H5)(MeCN){κ(P)-Ph2PCH2CH═CH2}(η2-CH2═C═CR1R2)][PF6] [R1 = R2 = Me (3); R1 = H, R2 = Ph (4); R1R2 = −(CH2)5– (5)]. On the other hand, the reaction of the pentamethylcyclopentadienyl-containing complex [Ru(η5-C5Me5)(MeCN){κ3(P,C,C)-Ph2PCH2CH═CH2}][OTf] (2) with allenes yields regio- and stereoselectively the complexes [Ru(η5-C5Me5){κ(P),η4-Ph2PCH2CH═CHC(R1R2)CH═CH2}][OTf] [R1 = R2 = Me (6); R1 = H, R2 = Ph (7); R1R2 = −(CH2)5– (8)] via the intermolecular coupling of allene and allyldiphenylphosphine ligands. The intermediate complex [Ru(η5-C5Me5)(MeCN){κ(P)-Ph2PCH2CH═CH2}{η2-CH2═C═CMe2}][OTf] (9) has been spectroscopically characterized. The structure of complex [Ru(η5-C5Me5){κ(P),η4-Ph2PCH2CH═CHC(Me)2CH═CH2}][{3,5-(CF3)2C6H3}4B] (6a) has been resolved by X-ray diffraction analysis.
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