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The far-infrared spectra of platinum(IV) complexes of the types cis- and trans-[PtX4L2](X = Cl, Br, or I; L = donor ligand) are assigned and discussed. For the trans complexes the halogen-sensitive modes occur near those of the related [PtX4]2– species whilst the ν(Pt–X) pattern for the cis complexes covers a wide range which includes that of ν(Pt–X) in bridging situations in platinum(II) compounds. Assignments are given for ν(Pt–P), ν(Pt–As), ν(Pt–S), and for the associated bending modes.

Raman and far-i.r. spectra are reported and assigned for the solid complexes Cr(CO)3(π-arene)(arene = benzene, aniline, toluene, methyl benzoate, anisole, and hexamethylbenzene) and M(CO)3(π-mesitylene)(M = Cr, Mo, or W). For the benzene complex, discussion is based upon the factor group, but in the other cases the molecular point-symmetry proves to be an adequate approximation. C3v local symmetry is an inadequate approximation when discussing the skeletal modes of complexes of monsubstituted arenes.

Raman and i.r. spectra of the title compounds are reported and assigned for both solids and solutions. ν(C–H) modes show correlationsplitting, but the remainder of the internal modes of the π-allyl ligands can be discussed in terms of Cs local symmetry. ν(C–C–C) modes of the allyl skeleton are placed ca. 1383 and 1020 cm.–1 in the parent complex.

The far-infrared spectra (70–400 cm.–1) of 36 thiourea and ethylenethiourea (imidazolidine-2-thione) complexes, embracing several different stereochemical types, are assigned and discussed. Metal–sulphur stretching frequencies, v(M–S), lie in the range 298–205 cm.–1 for the transition-metal complexes, and vary with co-ordination number and electron configuration in the manner now familiar from the behaviour of metal–hylogen stretching frequencies, v(M–X). For Group metals v(M–S) has been found as low as 170 cm.–1. The similarity between the spectra of thiourea complexes and those of thiocyanates has led to an assignment of the published data for thiocyanates. Some interesting variations in halogen-sensitive vibrations have been encountered.

I.r. spectra (70–4000 cm.–1) of nickel complexes of the type [Ni(S2C2R2)2]n–(R = H, CF3, or CN) and of [M(S2C2(CN)2)2]n–(M = Co, Cu, Zn, Pd, or Pt) are discussed. Vibrations containing a large (ν(M–S) contribution are found in the range 465–295 cm.–1. Frequency and intensity variations are consistent with the molecular orbital description of the bonding.For dithiophosphate complexes of three types of stereochemistry ν(M–S) is assigned in the region 330–220 cm.–1; the variation is mainly due to the differing masses of the metal.These results, together with other published work, lead to correlations for ν(M–S) for various ligands in the range 504–205 cm.–1.

The far-infrared spectra of some halogenocuprates of the types [CuX4]2–(planar and tetrahedral), [Cu2X6]2–, CsCuX3, and M2ICuCl4,2H2O have been studied. Complexes of the type CuX2L2(X = Cl or Br; L = donor ligand) are also considered. v(Cu–Cl) lies in the range 368—222 cm.–1 and v(Cu–Br) between 278 and 168 cm.–1. The spectra admit of a consistent interpretation without the need to postulate the presence of v(Cu–X) modes in the normal region due to stretching of copper–halogen “long” bonds. Bridging v(Cu–X) frequencies have been assigned but the range is severely overlapped by that of terminal v(Cu–X).

The ν(CO) spectra of Mo(CO)4 bipy (bipy = 2,2′-bipyridyl), cis-[W(CO)2{o-C6H4(PEt2)2}2],Cr(CO)3(π-mesitylene), and Cr(CO)3(π-C6H5·CO2Me) are examined in solution in n-hexane–chloroform or –nitrobenzene mixtures; the ν(NO) spectrum of Fe(NO)(S2CNMe2)2 is studied in benzene–nitromethane mixtures. Structure observed on the ν(CO) bands is discussed in terms of formation of solvent–solute complexes.

Raman and i.r. spectra are reported and assigned for X2Sn[Co(CO)4]2,X2Sn[Fe(CO)2(π-C5H5)]2(X = Cl, Br, and I), and M-SnCl3, (M = Mo(CO)3(π-C5H5); Rh(NBD)2; Ir(COD)2), and for a number of related compounds. Metal–metal stretching frequencies are in the range 165–235 cm.–1 and are intense in the Raman spectra.

Vibrational frequencies and force constants are reported for the ions [MCl6]2–(M = Ti, Zr, or Hf). An error in the early literature is corrected.