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 = <i>p</i>-cymene) with an excess of allyldiisopropylphosphane (ADIP) leads to the complex [RuCl­(η⁶-C₁₀H₁₄)­{κ²(<i>P</i>,<i>C</i>)-<i>i</i>Pr₂PCH₂CH­(<i>i</i>Pr₂PCH₂CHCH₂)­CH₂}]^<b>+</b> (<b>1</b>^<b>+</b>), which presents a new bidentate κ²(<i>P</i>,<i>C</i>) ligand. The same cationic complex can be prepared by nuclephilic attack of 1 equiv of the free ADIP at the coordinated κ³(<i>P</i>,<i>C</i>,<i>C</i>)-<i>i</i>Pr₂PCH₂CHCH₂ ligand in [RuCl­(η⁶-C₁₀H₁₄)­{κ³(<i>P</i>,<i>C</i>,<i>C</i>)-<i>i</i>Pr₂PCH₂CHCH₂}]^<b>+</b> (<b>3</b>^<b>+</b>). Addition of different phosphane ligands to complex <b>3</b>^<b>+</b> allows to the synthesis of ruthenium complexes with new bidentate ligands κ²(<i>P</i>,<i>C</i>). The unusual complexes [Ru­{κ³(<i>P</i>,<i>C</i>,<i>S</i>)<i>-i</i>Pr₂PCH₂CH­(SR)­CH₂}­(η⁶-C₁₀H₁₄)]^<b>+</b> (<b>11a</b>–<b>c</b>^<b>+</b>) containing new κ³(<i>P</i>,<i>C</i>,<i>S</i>)<i></i> ligands can be obtained by the reaction of <b>3</b>^<b>+</b> with anionic nucleophiles RS^–. For comparative purposes, the indenyl complex [Ru­(η⁵-C₉H₇)­{κ³(<i>P</i>,<i>C</i>,<i>C</i>)-<i>i</i>Pr₂PCH₂CHCH₂}­(PPh₃)]^<b>+</b> (<b>8</b>^<b>+</b>) has been also prepared and differences in the reactivities of cationic complexes <b>3</b>^<b>+</b> and <b>8</b>^<b>+</b> toward nucleophiles are pointed out