C鈥揌 versus O鈥揌 Bond Activation in Phosphino-alcohol Ligands: Synthesis of the 伪-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{魏2(P,C)-Ph2PC6H4C(R)OH}

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• 作者：Alba E. D铆az-脕lvarez ; Cristian Vidal ; Francisco J. Su谩rez ; Josefina D铆ez ; Victorio Cadierno ; Pascale Crochet
• 刊名：Organometallics
• 出版年：2015
• 出版时间：August 10, 2015
• 年：2015
• 卷：34
• 期：15
• 页码：3670-3677
• 全文大小：400K
• ISSN：1520-6041

文摘

The coordination of the phosphino-alcohol ligands 2-Ph₂PC₆H₄CH(R)OH (R = H, Me) onto an arene-ruthenium(II) fragment gave rise to the formation of complexes of general formula [RuCl₂{2-Ph₂PC₆H₄CH(R)OH}(畏⁶-arene)] (R = H, arene = C₆H₆ (3a), p-cymene (3b), mesitylene (3c), C₆Me₆ (3d); R = Me, arene = p-cymene (5b)). In solution, different isomers were observed depending on the solvent polarity. They arise from the different coordination modes adopted by the phosphino-alcohol: (i) the classical 魏¹-P mode through the selective coordination of the phosphorus atom, (ii) the establishment of both Ru鈥揚 and Cl路路路路H鈥揙 interactions, and (iii) the P,O-chelate formation. Treatment of these species with NaPF₆ led to the selective formation of the corresponding cationic species [RuCl{魏²-(P,O)-2-Ph₂PC₆H₄CH(R)OH}(畏⁶-arene)][PF₆] 6a鈥?b>d and 7b, respectively. Unexpectedly, under basic conditions these cationic compounds evolved into the neutral 伪-hydroxy-alkyl derivatives [RuCl{魏²-(P,C)-Ph₂PC₆H₄C(R)OH}(畏⁶-arene)] through a formal C鈥揌 bond activation process.