Electrospray mass spectrometry and X-ray crystallography studies of divalent metal ion complexes of tris (2-pyridylmethyl) amine

Craig S. Allen, Chang Lin Chuang, Mark Cornebise, James W. Canary

Research output: Contribution to journalArticlepeer-review

Abstract

Coordination complexes of tris(2-pyridylmethyl)amine (TPA) were prepared and characterized including [Zn(TPA)X]ClO4 (X = Cl, Br, I), [Cu(TPA)Br]ClO4, [Cd(TPA)Br2], [Cd(TPA) (H2O) (NO3]NO3, [Cd(TPA)I2], [Co9TPA)Cl2], [Fe(TPA)Cl2] and [Mn(TPA) Cl2] The solid-state structures of Zn(TPA)ClClO4 (monoclinic space group, P21/c; a = 14.733(3), b = 9.408(2), c = 29.722(4) A ̊, β=90.65(1)°; V=4119(1) A ̊3; Z=8, Zn(TPA)IClO4 (triclinic space group, P1; a = 14.435(3), b = 17.69(4), c = 9.745(2) A ̊, α=100.36(2), β=91.40(2), γ=114.62(1)°; V=2134(2) A ̊3; Z=4) and Cu(TPA)BrClO4 (monoclinic space group, P21/c; a=14.555(3), b=9.519(2), c=30.024(3) A ̊, β=91.66(1)°; V=4158(1) A ̊3; Z=8), contain trigonal bypyramidal metal ions with halide coordinated in an apical position. The X-ray structure of [Cd(TPA)(H2O)(NO3)]NO3 (monoclinic space group, P21/n; a=15.415(4), b=9.333(2), c=17.429(4) a ̊, β=99.39(2)°; V=2474(2) A ̊3; Z=4) contains a seven-coordinate cadmium ion including a bidentate nitrate anion and a water molecule as ligands. The X-ray structure of [Cd(TPA)I2] (monoclinic space group, P21/n; a=10.383(2), b=13.813(2), c=15.391(1) A ̊, β=106.07(1)°; V=2121.1(5) A ̊3; Z=4) contains a cadmium ion with an approximately octahedral geometry. In this structure, the TPA ligand is conformationally distorted in order to accomodate the octahedral coordination geometry. The convenient new technique, electrospray mass spectrometry (ESI-MS), provided mass spectra consistent with X-ray and spectroscopic data. Mass analysis of solutions containing added competing anions was also consistent with solution data.

Original languageEnglish (US)
Pages (from-to)29-37
Number of pages9
JournalInorganica Chimica Acta
Volume239
Issue number1-2
DOIs
StatePublished - Nov 1995

Keywords

  • Cadmium complexes
  • Crystal structures
  • Electrospray mass spectrometry
  • Polydentate amine complexes
  • Zinc complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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