Organoruthenium Complexes Containing New Phosphorus–Carbon and Phosphorus–Carbon–Sulfur Ligands Generated in the Coordination Sphere by Nucleophilic Addition Reactions

The reaction of the dimeric complex [RuCl­(μ-Cl)­(η6-C10H14)]2 (C10H14 = p-cymene) with an excess of allyldiisopropylphosphane (ADIP) leads to the complex [RuCl­(η6-C10H14)­{κ2(P,C)-iPr2PCH2CH­(iPr2PCH2CHCH2)­CH2}]+ (1+), which presents a new bidentate κ2(P,C) ligand. The same cationic complex can be prepared by nuclephilic attack of 1 equiv of the free ADIP at the coordinated κ3(P,C,C)-iPr2PCH2CHCH2 ligand in [RuCl­(η6-C10H14)­{κ3(P,C,C)-iPr2PCH2CHCH2}]+ (3+). Addition of different phosphane ligands to complex 3+ allows to the synthesis of ruthenium complexes with new bidentate ligands κ2(P,C). The unusual complexes [Ru­{κ3(P,C,S)-iPr2PCH2CH­(SR)­CH2}­(η6-C10H14)]+ (11a–c+) containing new κ3(P,C,S) ligands can be obtained by the reaction of 3+ with anionic nucleophiles RS–. For comparative purposes, the indenyl complex [Ru­(η5-C9H7)­{κ3(P,C,C)-iPr2PCH2CHCH2}­(PPh3)]+ (8+) has been also prepared and differences in the reactivities of cationic complexes 3+ and 8+ toward nucleophiles are pointed out.