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Infrared intensity and nuclear magnetic resonance studies of some group VIB metal chalcocarbonyl complexes

McGill University
Publication Date
  • Carbonyl Compounds.
  • Nuclear Magnetic Resonance Spectroscopy.
  • Ultraviolet Spectroscopy.
  • Chemistry
  • Physics


Some physicochemical properties of several series of transition metal chalcocarbonyls such as ((eta)('6)-C(,6)H(,6))Cr(CO)(,2)(CX) and Cr(CO)(,5)(CX) (X = O, S, Se) have been investigated. In particular, the infrared, ('13)C and ('17)O nuclear magnetic resonance and ultraviolet spectra have been examined. The results show that the order of (sigma)-donor and (pi)-acceptor capabilities of the ligands is CO CS. The M((pi)) (--->) CX((pi)*) ultraviolet charge-transfer bands are shown to correlate with the respective (mu)'(,MCX) and ('13)C NMR data. Also, the ('13)C NMR chemical shifts and GQVFF force constants are found to be highly correlated. The ('17)O NMR spectra of the metal chalcocarbonyl complexes display chemical shifts in the opposite direction to the corresponding ('13)C ones. No correlation is found between the ('17)O shieldings and the other spectroscopic data. Reaction of Cr(CO)(,5)(CX) (X = S, Se) with halide ions (Y('-)) afforded mixtures of {Cr(CO)(,5)Y}('-) and trans-{Cr(CO)(,4)(CX)Y}('-) while Cr(CO)(,5)(CS) reacted with cyclohexylamine to give Cr(CO)(,5)(CNC(,6)H(,11)). The similarities and differences in the physicochemical behaviour of the metal chalcocarbonyls compared to related systems are discussed in the light of the different bonding patterns.

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