Please use this identifier to cite or link to this item:
Title: Large bite bisphosphite, 2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2: synthesis, derivatization, transition metal chemistry and application towards hydrogenation of olefins
Keywords: Derivatives
Synthesis (Chemical)
Transition Metal Compounds
Issue Date: 2007
Publisher: Elsevier
Citation: Journal of Organometallic Chemistry 692(8), 1683-1689
Abstract: Large bite bisphosphite ligand, 2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2 (2), is obtained by reacting chlorophosphite, {-OC10H6(μ-S)C10H6O-}PCl (1) with 2,6-pyridinedimethanol in presence of triethylamine.Treatment of 2 with aqueous solution of H2O2 or elemental sulfur resulted in the formation of bis(oxide) or bis(sulfide) derivatives, 2,6-C5H3N{CH2OP(E)(–OC10H6)(μ-S)(C10H6O–)}2 (3, E = O; 4, E = S) in quantitative yield.The 10-membered cationic chelate complex, [RuCl(η6-C10H14)η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2-κP,κP]Cl (5) is produced in the reaction between [Ru(p-cymene)(μ-Cl)(Cl)]2 and bisphosphite 2, whereas the neutral chelate complex, cis-[Rh(CO)Cl{2,6-C5H3N{CH2OP(–OC10H6(μ-S)C10H6O–)}2}-κP,κP] (6) is isolated in the reaction of 2 with 0.5 equiv.of [Rh(CO)2Cl]2.Compound 2 on treatment with M(COD)Cl2 (M = Pd, Pt) produce the chelate complexes, [MCl2{η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2}-κP,κP] (7, M = Pd;10, M = Pt).Similarly the reaction of bisphosphite 2 with Pd(COD)MeCl affords cis-[PdMe(Cl)η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2-κP,κP] (8).Treatment of 2 with [Pd(η3- C3H5)Cl]2 in the presence of AgClO4 furnish the cationic complex, [Pd(η3-C3H5)η2-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2-κP,κP]ClO4 (9). The binuclear complex, [Au2Cl2{2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2}-κP,κP] (11) is obtained in the reaction of compound 2 with two equiv. of AuCl(SMe2), where the ligand exhibits bridged bidentate mode of coordination. All the complexes are characterized by the 1H NMR, 31P NMR, elemental analysis and mass spectroscopy data. The cationic ruthenium complex 5 is proved to be an active catalyst for the hydrogenation of styrene and α-methyl styrene.
ISSN: 0022-328X
Appears in Collections:Article

Files in This Item:
File Description SizeFormat 
5265-2.pdf402.92 kBAdobe PDFThumbnail

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.