• Joel T Mague

      Articles written in Journal of Chemical Sciences

    • 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)

      Maravanji S Balakrishna D Suresh Joel T Mague

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      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.

    • A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation

      Guddekoppa S Ananthnag Joel T Mague Maravanji S Balakrishna

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      The hydrolysis of cis-{ClP(𝜇-N$^t$Bu)2P(NH$^t$Bu)} (1) produced a mixed PIII/PV derivative of cyclodiphosphazane, cis-{($^t$BuNH)P(𝜇-N$^t$Bu)2P(O)H} (2). The treatment of 2 with elemental selenium resulted in the formation of the monoselenide, trans-{($^t$BuNH)P(Se)(𝜇-N$^t$Bu)2P(O)H} (3) in good yield. The reactions of two equivalent of 2 with [Pd(𝜇-Cl)(𝜂3-C3H5)]2 or [Ru(𝜂6-𝑝-cymene)(𝜇-Cl)Cl]2 in dichloromethane afforded corresponding mononuclear complexes, [(𝜂3-C3H5)PdCl{($^t$BuNH)P(𝜇-N$^t$Bu)2P(O)H}] (4) and [((𝜂6-𝑝-cymene)RuCl2){($^t$BuNH)P(𝜇-N$^t$Bu)2P(O)H}] (5). The treatment of 2 with M(COD)Cl2 (M = Pd and Pt) in dichloromethane at room temperature gave [MCl2{($^t$BuNH)P(𝜇-N$^t$Bu)2P(O)H}2] (6 M = Pd; 7 M = Pt) in good yield. Owing to the cis/trans isomerisation of the cyclodiphosphazane rings, the complexes 6 and 7 exist as a mixture of two isomers. Various NMR spectroscopic techniques were employed for structural elucidation. The molecular structures of 5 and 7 were established by single crystal X-ray crystallographic studies.

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