Force constant calculatiom for the in-plane vibrations of complexes cis-[MX2(CO)2]n- (for n = 0, MX = PtCl or PtBr; for n = 1, MX = RhCl, RhBr or IrCl)

P. L. Goggin, J. Mink

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14 Citations (Scopus)

Abstract

Force constants for planar complexes cis-[MX2(CO)2]O or- (MX - RhCl, RhB R, IrCl, PtC1 and PtBr) have been calculated using a modified mlence force field, with constrained off -diagonal force constant based on [MX4]- and [MX2(CO])- (M = Pt or Pd) studies. The MC stretching force constant are proportionately more sensitive than those for CO, but for members of the same transition series the trends are in fair agreement with the proportionate chat in bond orders. For the platinum complexes. incorporation of PtC n. m.r. coupling data improves the agreement. As between [PtCl2CO]- and [PdCI2CO]-, the lowering of the metal-carbon stretching force constant between [IrCl2(CO)2]- and [RhCl2(CO)2] is much greater than for metal-chlorine and it is suggested that the lower availability of 4d orbitals than 5d strongly affects the RhCO σ-bonding as well as the π-bonding.

Original languageEnglish
Pages (from-to)225-230
Number of pages6
JournalInorganica Chimica Acta
Volume34
Issue numberC
DOIs
Publication statusPublished - 1979

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Carbon Monoxide
Vibration
Stretching
vibration
Metals
Chlorine
Platinum
Availability
Carbon
metals
field theory (physics)
chlorine
availability
platinum
trends
orbitals
carbon

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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title = "Force constant calculatiom for the in-plane vibrations of complexes cis-[MX2(CO)2]n- (for n = 0, MX = PtCl or PtBr; for n = 1, MX = RhCl, RhBr or IrCl)",
abstract = "Force constants for planar complexes cis-[MX2(CO)2]O or- (MX - RhCl, RhB R, IrCl, PtC1 and PtBr) have been calculated using a modified mlence force field, with constrained off -diagonal force constant based on [MX4]- and [MX2(CO])- (M = Pt or Pd) studies. The MC stretching force constant are proportionately more sensitive than those for CO, but for members of the same transition series the trends are in fair agreement with the proportionate chat in bond orders. For the platinum complexes. incorporation of PtC n. m.r. coupling data improves the agreement. As between [PtCl2CO]- and [PdCI2CO]-, the lowering of the metal-carbon stretching force constant between [IrCl2(CO)2]- and [RhCl2(CO)2] is much greater than for metal-chlorine and it is suggested that the lower availability of 4d orbitals than 5d strongly affects the RhCO σ-bonding as well as the π-bonding.",
author = "Goggin, {P. L.} and J. Mink",
year = "1979",
doi = "10.1016/S0020-1693(00)94705-4",
language = "English",
volume = "34",
pages = "225--230",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier BV",
number = "C",

}

TY - JOUR

T1 - Force constant calculatiom for the in-plane vibrations of complexes cis-[MX2(CO)2]n- (for n = 0, MX = PtCl or PtBr; for n = 1, MX = RhCl, RhBr or IrCl)

AU - Goggin, P. L.

AU - Mink, J.

PY - 1979

Y1 - 1979

N2 - Force constants for planar complexes cis-[MX2(CO)2]O or- (MX - RhCl, RhB R, IrCl, PtC1 and PtBr) have been calculated using a modified mlence force field, with constrained off -diagonal force constant based on [MX4]- and [MX2(CO])- (M = Pt or Pd) studies. The MC stretching force constant are proportionately more sensitive than those for CO, but for members of the same transition series the trends are in fair agreement with the proportionate chat in bond orders. For the platinum complexes. incorporation of PtC n. m.r. coupling data improves the agreement. As between [PtCl2CO]- and [PdCI2CO]-, the lowering of the metal-carbon stretching force constant between [IrCl2(CO)2]- and [RhCl2(CO)2] is much greater than for metal-chlorine and it is suggested that the lower availability of 4d orbitals than 5d strongly affects the RhCO σ-bonding as well as the π-bonding.

AB - Force constants for planar complexes cis-[MX2(CO)2]O or- (MX - RhCl, RhB R, IrCl, PtC1 and PtBr) have been calculated using a modified mlence force field, with constrained off -diagonal force constant based on [MX4]- and [MX2(CO])- (M = Pt or Pd) studies. The MC stretching force constant are proportionately more sensitive than those for CO, but for members of the same transition series the trends are in fair agreement with the proportionate chat in bond orders. For the platinum complexes. incorporation of PtC n. m.r. coupling data improves the agreement. As between [PtCl2CO]- and [PdCI2CO]-, the lowering of the metal-carbon stretching force constant between [IrCl2(CO)2]- and [RhCl2(CO)2] is much greater than for metal-chlorine and it is suggested that the lower availability of 4d orbitals than 5d strongly affects the RhCO σ-bonding as well as the π-bonding.

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JO - Inorganica Chimica Acta

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