Vibrational Spectra of PtCO and Pt(CO)₂ Isolated in Solid Argon:  Trends in Unsaturated Group 10 Metal Carbonyl Molecules

The infrared spectrum of PtCO isolated in solid argon has been reinvestigated. Isotopic data on ν 1, ν 2, ν 3, 2ν 1, and ν 1 + ν 3 have been measured in the near- and far-infrared regions. This enables a complete harmonic force-field calculation based on a linear geometry, in agreement with all theoretical predictions. Comparisons of spectroscopic parameters for the NiCO, PdCO, and PtCO series experimental and theoretical binding energies are also presented. These results show that the perturbations of the CO ligand (CO bond force constants and ν 1 frequency shifts) are unreliable indicators of the evolution of the metal−ligand interaction energies, contrary to the metal−carbon force constant. Comparison with theoretical predictions of the fundamental frequencies indicates a systematic underestimation of the bending frequencies, especially sensitive for the heavy atom monocarbonyls. Similarly, the IR spectrum of Pt(CO) 2 has been studied, enabling the determination of the ν 1, ν 2, ν 3, ν 4, and ν 6 fundamentals of this molecule and a discussion of the evolution of the Pt−C and C⋮O force constants with the coordination number. Complementary results concerning Pt(CO) n ( n = 3, 4) are also presented.