Organoruthenium Complexes Containing New Phosphorus鈥揅arbon and Phosphorus鈥揅arbon鈥揝ulfur Ligands Generated in the Coordination Sphere by Nucleophilic Addition Reactions

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• 作者：Isaac Garcı ; &#769 ; a de la Arada ; Josefina Dı ; &#769 ; ez ; M. Pilar Gamasa ; Elena Lastra
• 刊名：Organometallics
• 出版年：2013
• 出版时间：August 12, 2013
• 年：2013
• 卷：32
• 期：15
• 页码：4342-4352
• 全文大小：467K
• 年卷期：v.32,no.15(August 12, 2013)
• ISSN：1520-6041

文摘

The reaction of the dimeric complex [RuCl(渭-Cl)(畏⁶-C₁₀H₁₄)]₂ (C₁₀H₁₄ = p-cymene) with an excess of allyldiisopropylphosphane (ADIP) leads to the complex [RuCl(畏⁶-C₁₀H₁₄){魏²(P,C)-iPr₂PCH₂CH(iPr₂PCH₂CH鈺怌H₂)CH₂}]⁺ (1⁺), which presents a new bidentate 魏²(P,C) ligand. The same cationic complex can be prepared by nuclephilic attack of 1 equiv of the free ADIP at the coordinated 魏³(P,C,C)-iPr₂PCH₂CH鈺怌H₂ ligand in [RuCl(畏⁶-C₁₀H₁₄){魏³(P,C,C)-iPr₂PCH₂CH鈺怌H₂}]⁺ (3⁺). Addition of different phosphane ligands to complex 3⁺ allows to the synthesis of ruthenium complexes with new bidentate ligands 魏²(P,C). The unusual complexes [Ru{魏³(P,C,S)-iPr₂PCH₂CH(SR)CH₂}(畏⁶-C₁₀H₁₄)]⁺ (11a鈥?b>c⁺) containing new 魏³(P,C,S) ligands can be obtained by the reaction of 3⁺ with anionic nucleophiles RS^{鈥?/sup>. For comparative purposes, the indenyl complex [Ru(畏5-C₉H₇){魏3(P,C,C)-iPr₂PCH₂CH鈺怌H₂}(PPh₃)]+ (8+) has been also prepared and differences in the reactivities of cationic complexes 3+ and 8+ toward nucleophiles are pointed out.}