Binary Dinitrogen Complexes of Rhodium, Rh(N2)n (where n = 1–4), in Low Temperature Matrices

Abstract

The products of the cocondensation reactions of Rh atoms with N2 and N2/Ar mixtures at 10 °K are investigated by matrix isolation infrared spectroscopy and are shown to be binary dinitrogen complexes of the form Rh(N2)n. Examination of the reaction products in pure 14N2, 15N2, 14N2/15N2, and in dilute Ar/14N2, Ar/14N2/15N2, and Ar/14N2/14N15N/15N2 matrices establish the values of n to be 1–4. Isotopic frequencies are computed for the NN stretching modes of the individual dinitrogen complexes on the basis of the Cotton–Kraihanzel (C.K.) force field approximation and are found to be in close agreement with observed values. Trends in the best fit C.K. force constants for Rh(N2)n (n = 1–4) and the thermodynamic stabilities of the individual complexes as indicated by the function ΔHcn, a measure of the enthalpy of decomposition, are discussed. Comparisons are made between Ni(N2)n and Rh(N2)n (where n = 1–4). The structure of Rh(N2)4 in solid nitrogen is shown to be that of a distorted tetrahedron. Calculations show that a site symmetry of D2d for Rh(N2)4 satisfactorily accounts for all of the spectral lines observed for the complex in nitrogen. In solid argon, Rh(N2)4 appears to have an approximately regular tetrahedral structure. The relationship between RhN2 and N2 chemisorbed on Rh metal is discussed and compared with the analogous Ni–, Pd–, and Pt–nitrogen systems.