15505nas a2200145 45000080041000002450054000412100048000952600008001433000016001514900008001675201504900175100002015224700003115244856008415275 2007 eng d00aLarge bite bisphosphite, 2,6-C5H3N{CH2OP(-OC10H6)0 aLarge bite bisphosphite 26C5H3N CH2OPOC10H6 cMAR a1683–16890 v6923 a

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-C10H142-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2PP]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}-κPP] (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, [MCl22-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2}-κPP] (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–)}2PP] (8).Treatment of 2 with [Pd(η3- C3H5)Cl]2 in the presence of AgClO4 furnish the cationic complex, [Pd(η3-C3H52-2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2PP]ClO4 (9). The binuclear complex, [Au2Cl2{2,6-C5H3N{CH2OP(–OC10H6)(μ-S)(C10H6O–)}2}-κPP] (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.

 

 

1 aPunji, Benudhar1 aBalakrishna, Maravanji, S. uhttps://library.ncl.res.in/content/large-bite-bisphosphite-26-c5h3nch2op-oc10h601387nas a2200169 4500008004100000245010600041210007000147260000800217300001400225490000800239520075000247100003100997700001701028700002001045700002001065856013201085 2010 eng d00aLarge-bite bisphosphite, 1,3-C6H4{OPOC10H6(μ-S)C10H6O}2: synthesis, copper(I), and gold(I) complexes0 aLargebite bisphosphite 13C6H4 OPOC10H6μSC10H6O 2 synthesis coppe cNOV a981–9860 v6953 a

Large-bite bisphosphite ligand 1,3-C6H4{OPOC10H6(μ-S)C10H6O}2 (3), is obtained by reacting chlorophosphonite {OC10H6(μ-S)C10H6O}PCl (2) with resorcinol in the presence of triethylamine. Treatment of 3 with CuCl in 1:1 molar ratio produces a 1D-coordination polymer [CuCl{(–OC10H6(μ-S)C10H6O–)P(–OC6H4O–)P(–OC10H6(μ-S)C10H6O–)}-κP,κP]∞ (4) in good yield. Similar reaction of 3 with two equivalents of AuCl(SMe2) affords a dinuclear complex, [Au2Cl2{(–OC10H6(μ-S)C10H6O–)P(–OC6H4O–)P(–OC10H6(μ-S)C10H6O–)}-κP,κP] (5). Single crystal X-ray structures of the ligand 3 and the complexes 4 and 5 are reported. The gold complex 5 shows dimeric structure supported by strong Au···Au aurophilic interactions.

1 aBalakrishna, Maravanji, S.1 aKumar, Pawan1 aPunji, Benudhar1 aMague, Joel, T. uhttps://library.ncl.res.in/content/large-bite-bisphosphite-13-c6h4opoc10h6%CE%BC-sc10h6o2-synthesis-copperi-and-goldi-complexes