• Mono-, di- and tetranuclear rhodium(I) complexes of morpholine and 𝑁-methylpiperazine functionalized cyclodiphosph(III)azanes, cis-[(${}^t$BuN-𝜇)2(PNC4H8X)2] (X = O, NMe)

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    • Keywords

       

      Bis(amido)cyclodiphosphazanes; rhodium(I); tetranuclear complexes; crystal structures; dirhodium(I) hydroxyl derivative; zwitterionic complex.

    • Abstract

       

      The reactions of cyclodiphosphazanes, cis-[(${}^t$BuN-𝜇)2(PNC4H8O)2] (1, R = NC4H8O; 2, R = NC4H8NMe ) (2) with [{RhCl(COD)}2] and [{RhCl(CO)2}2] are described. The reactions of 1 or 2 with [{RhCl(COD)}2] in 2:1 molar ratio yielded the mononuclear complexes [(COD)RhCl{(𝜇-N$^t$BuP)2(NC4H8X)2}] (3, X = O; 4, X = NMe) in good yield. Treatment of one equivalent of [{RhCl(CO)2}2] with four equivalents of 1 or 2 produced the trans-[(CO)RhCl{(𝜇-N$^t$BuP)2(NC4H8X)2}2] (5, X = O; 6, X = NMe) complexes as pale yellow solids. On changing the molar ratio of [{RhCl(CO)2}2] and 1 or 2 from 1:4 to 1:1 resulted in the formation of tetranuclear complexes [{(CO)Rh(𝜇-Cl)(𝜇-N$^t$BuP)(NC4H8X)$\}_4$] (7, X = O; 8, X = NMe) under similar reaction conditions. The tetranuclear rhodium(I) complex 8 upon stirring with wet acetonitrile or in the presence of four equivalents of water at room temperature afforded a novel hydroxo bridged zwitterionic dirhodium(I) complex [{(ClRh(CO))2(𝜇-OH)(MeNC4H8N)(𝜇-N$^t$BuP)2(NC4H8NHMe)}] (9). The crystal structures of 5, 6 and 9 were established by single crystal X-ray diffraction studies.

    • Author Affiliations

       

      Maravanji S Balakrishna1 D Suresh1 Joel T Mague2

      1. Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India
      2. Department of Chemistry, Tulane University, New Orleans, LA 70118, USA
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  • Journal of Chemical Sciences | News

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