Ruthenium(II), copper(I) and silver(I) complexes of large bite bisphosphinite, bis(2-diphenylphosphinoxynaphthalen-1-yl)methane: Application of Ru(II) complexes towards the hydrogenation of styrene and phenylacetylene |
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Authors: | Benudhar Punji Maravanji S Balakrishna |
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Institution: | a Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India b Department of Chemistry, Tulane University, New Orleans, LA 70118, USA |
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Abstract: | Ruthenium(II), copper(I) and silver(I) complexes of large bite bisphosphinite Ph2P{(-OC10H6)(μ-CH2)(C10H6O-)}PPh2 (1) are described. Reactions of bisphosphinite 1 with Ru(η6-p-cymene)(μ-Cl)Cl]2 and RuCl2(PPh3)3 afford mono- and bis-chelate complexes RuCl(η6-p-cymene){η2-Ph2P{(-OC10H6)(μ-CH2)(C10H6O-)}PPh2-κP,κP}]Cl (2) and trans-RuCl2{η2-Ph2P{(-OC10H6)(μ-CH2)(C10H6O-)}PPh2-κP,κP}2] (3), respectively. Treatment of 1 with CuX (X = Cl, Br and I) furnish 10-membered chelate complexes of the type Cu(X){η2-Ph2P(-OC10H6)(μ-CH2)(C10H6O-)PPh2-κP,κP}] (4, X = Cl; 5, X = Br; 6, X = I), whereas Cu(MeCN)4]PF6 affords a bis-chelated cationic complex Cu{η2-Ph2P(-OC10H6)(μ-CH2)(C10H6O-)PPh2-κP,κP}2]PF6] (7). Reaction between 1 and AgOTf produce both mono- and bis-chelated complexes Ag{η2-Ph2P(-OC10H6)(μ-CH2)(C10H6O-)PPh2-κP,κP}(SO3CF3)] (8) and Ag{η2-Ph2P(-OC10H6)(μ-CH2)(C10H6O-)PPh2-κP,κP}2]SO3CF3] (9), respectively; whereas the similar reaction of 1 withAg(OTf)PPh3] affords chelate complex of the type Ag{η2-Ph2P(-OC10H6)(μ-CH2)(C10H6O-)PPh2-κP,κP}(PPh3)(SO3CF3)] (10). All the complexes were characterized by 1H NMR, 31P NMR, elemental analysis and mass spectrometry, including low-temperature NMR studies in the case of silver complexes. The molecular structures of 4 and 6 are determined by X-ray diffraction studies. Ruthenium complexes 2 and 3 promote catalytic hydrogenation of styrene and phenylacetylene with good turnover numbers. |
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Keywords: | Bisphosphinite Chelate complexes Ruthenium(II) copper(I) and silver(I) complexes Crystal structures Hydrogenation reactions |
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