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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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Title 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
 
Creator PUNJI, BENUDHAR
MAGUE, JOEL T
BALAKRISHNA, MS
 
Subject reaction kinetics
copper compounds
crystal structure
x-ray diffraction
hydrogenation
 
Description 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 with[Ag(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.
 
Publisher Elsevier
 
Date 2009-03-19T07:24:33Z
2011-11-25T19:35:20Z
2011-12-26T13:07:34Z
2011-12-27T05:55:35Z
2009-03-19T07:24:33Z
2011-11-25T19:35:20Z
2011-12-26T13:07:34Z
2011-12-27T05:55:35Z
2006
 
Type Article
 
Identifier Journal of Organometallic Chemistry 691(20), 4265-4272
0022-328X
http://dx.doi.org/10.1016/j.jorganchem.2006.06.040
http://hdl.handle.net/10054/998
http://dspace.library.iitb.ac.in/xmlui/handle/10054/998
 
Language en