• Patrick J Carroll

      Articles written in Journal of Chemical Sciences

    • Study of reactivity ofp-cymene ruthenium(II) dimer towards diphenyl-2-pyridylphosphine: Synthesis, characterization and molecular structures of [(η6-p-cymene)RuCl2(PPh2Py)] and [(η6-p-cymene)RuCl(PPh2Py)]BF4

      R Lalrempuia Patrick J Carroll Mohan Rao Kollipara

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      The reaction of [(η6-p-cymene)Ru(μCl)2Cl2] with functionalized phosphine viz, diphenyl-2-pyridylphosphine yielded complexes of the type: (a) P-bonded complex [(η6-p-cymene)RuCl2(PPh2Py)] (1), (b) P-, N-chelated complex [(η6-p-cymene)RuCl-(PPh2Py)]BF4 (2) and [RuCl2(PPh2Py)2] (3) resulting from the displacement of thep-cymene ligand. These complexes were characterized by1H NMR,31P NMR and analytical data. The structures of complexes1 and2 have been confirmed by single crystal X-ray diffraction study. Complex1 crystallised in triclinic space groupP 1 witha = 10.9403 (3) Å,b= 13.3108 (3) Å,c= 10-5394 (10) Å, α=88.943 (2)°, β = 117.193 (2)°, γ= 113.1680 (10)°, Z=2 andV= 1230.39 (5) Å3. The complex2 crystallises in monoclinic space group P21 witha = 9.1738 (4) Å,b = 14.0650 (6) s, c = 10.7453 (5) Å, β= 106.809 (1)°, Z = 2 andV= 1327.22 (10) Å3

    • Substitution reactions of diphenyl-2-pyridylphosphine with [(η5-C5Me5)M(μ-Cl)Cl]2 (M = Rh or Ir) dimers: Isolation of mono–, di– and chelating complexes

      Padavattan Govindaswamy Patrick J Carroll Yurij A Mozharivskyj Mohan Rao Kollipara

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      The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5) IrCl21-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5)IrCl21-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3, [(η5-C5Me5)IrCl21-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+6 are established by single-crystal X-ray diffraction methods

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