@article {42751, title = {Large bite bisphosphite, 2,6-C5H3N{CH2OP(-OC10H6)}, journal = {Journal of Organometallic Chemistry}, volume = {692}, year = {2007}, month = {MAR}, pages = {1683{\textendash}1689}, type = {Article}, abstract = {

Large bite bisphosphite ligand, 2,6-C5H3N{CH2OP({\textendash}OC10H6)(μ-S)(C10H6O{\textendash})}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)({\textendash}OC10H6)(μ-S)(C10H6O{\textendash})}2\ (3, E\ =\ O;\ 4, E\ =\ S) in quantitative yield.The 10-membered cationic chelate complex, [RuCl(η6-C10H142-2,6-C5H3N{CH2OP({\textendash}OC10H6)(μ-S)(C10H6O{\textendash})}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({\textendash}OC10H6(μ-S)C10H6O{\textendash})}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({\textendash}OC10H6)(μ-S)(C10H6O{\textendash})}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({\textendash}OC10H6)(μ-S)(C10H6O{\textendash})}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({\textendash}OC10H6)(μ-S)(C10H6O{\textendash})}2PP]ClO4\ (9). The binuclear complex, [Au2Cl2{2,6-C5H3N{CH2OP({\textendash}OC10H6)(μ-S)(C10H6O{\textendash})}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.

}, doi = {10.1016/j.jorganchem.2006.12.037}, author = {Punji, Benudhar and Balakrishna, Maravanji S.} } @article {42748, title = {Large-bite bisphosphite, 1,3-C6H4{OPOC10H6(μ-S)C10H6O}2: synthesis, copper(I), and gold(I) complexes}, journal = {Journal of Organometallic Chemistry}, volume = {695}, year = {2010}, month = {NOV}, pages = {981{\textendash}986}, abstract = {

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{({\textendash}OC10H6(μ-S)C10H6O{\textendash})P({\textendash}OC6H4O{\textendash})P({\textendash}OC10H6(μ-S)C10H6O{\textendash})}-κP,κP]$\infty$ (4) in good yield. Similar reaction of 3 with two equivalents of AuCl(SMe2) affords a dinuclear complex, [Au2Cl2{({\textendash}OC10H6(μ-S)C10H6O{\textendash})P({\textendash}OC6H4O{\textendash})P({\textendash}OC10H6(μ-S)C10H6O{\textendash})}-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{\textperiodcentered}{\textperiodcentered}{\textperiodcentered}Au aurophilic interactions.

}, author = {Balakrishna, Maravanji S. and Kumar, Pawan and Punji, Benudhar and Mague, Joel T.} }