Electronic spectra of some tetragonal complexes of rhodium(III), iridium(III) and platinum(IV) [1

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Solution electronic spectral data are reported for 30 tetragonal complexes of the types trans-M(en) 2X n+ 2, M(NH 3) 5X n+ (M = Rh(III), Ir(III), or Pt(IV); X = Cl, Br, or I); trans-M(NH 3) 4X n+ 2 (M = Rh(III) or Pt(IV); X = Cl, Br, or I); trans-PtL 4X 2− 2 (L = CN − or NO − 2, X = Cl or Br); and Pt(CN) 5X 2− (X = Cl, Br, or I). These data are interpreted in terms of ligand field (LF) excited states in C 4v or D 4h symmetry and ligand to metal charge transfer (LMCT) excited states involving the halide ligands. Intensity patterns among the LMCT transitions of intermediate intensity are rationalized by including halide spin-orbit coupling in excited configurations. Trends in LF and LMCT excited state energies are discussed.