Hemilabile 尾-Aminophosphine Ligands Derived from 1,3,5-Triaza-7-phosphaadamantane: Application in Aqueous Ruthenium Catalyzed Nitrile Hydration

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• 作者：Wei-Chih Lee ; Jeremiah M. Sears ; Raphel A. Enow ; Kelly Eads ; Donald A. Krogstad ; Brian J. Frost
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：February 18, 2013
• 年：2013
• 卷：52
• 期：4
• 页码：1737-1746
• 全文大小：427K
• 年卷期：v.52,no.4(February 18, 2013)
• ISSN：1520-510X

文摘

A series of 尾-aminophosphines derived from 1,3,5-triaza-7-phosphaadamantane (PTA) are described. PTA-CHPhNHPh (1), PTA-CH(p-C₆H₄OCH₃)NHPh (2), and PTA-CPh₂NHPh (3) were prepared in good yield (62鈥?7%) by reaction of lithiated PTA with the corresponding imine followed by hydrolysis. Compounds 1 and 2 were synthesized as pairs of diastereomers which were separated by successive recrystallization from THF/hexane. Compounds 1鈥?b>3 are somewhat soluble in water (S₂₅^o = 4.8 (1), 4.9 (2), 2.7 (3) g/L). Upon coordination to Ru(II) arene centers both monodentate (魏¹-P) [RuCl₂(畏⁶-toluene)(1鈥?b>3)] and bidentate (魏²-P,N) [RuCl(畏⁶-toluene)(1鈥?b>3)]Cl coordination modes were observed. Ru(II) arene complexes 4鈥?b>6 exhibited hemilabile behavior transitioning between 魏¹-P and 魏²-P,N coordination upon change in solvent or addition of a coordinating ligand such as Cl^{鈥?/sup> or CH₃CN. Complexes (4鈥?b>6) were found to be active air stable catalysts for the aqueous phase hydration of various nitriles with TOF up to 285 h鈥? and TON of up to 97鈥?00 observed.}