Configurations of some complexes of rhenium, ruthenium, osmium, rhodium, iridium, and platinum halides with mono(tertiary phosphines) and mono(tertiary arsines)

Abstract

Ir; X = CI or Br; L = mono(tertiary phosphine) or mono(tertiary arsine)] are described. The former group g e n era I I y h av e transc o n f i g u ratio n s a n d the I at t e r meridional.The structural configurations of the complexes with tzs4 metal electron configurations are reliably determined by I H n.m.r. spectral measurements. These have shown that the complexes [ReCi,( PR3),] have mer-configurations and the complexes [OsCI,( PR, ), ] probably have trans-configurations. For complexes with t 2: configurations only broad IH n.m.r. spectra were observed, which, except for [RuCI,(PMe,Ph),],were of no use for structural assignments. However, e.s.r. spectral measurements have confirmed the suggested configurations for the t i : complexes.Far-i.r. studies in the solid state have in general supported the above configurations but are not definitive, especially where complexes of transition elements of the Third Period are concerned.

On the Blue Complexes Formed in Acidic Solutions of Hexaammineruthenium(II)

“…[Ru"'(NH,),CI,] was insoluble in all common solvents. Its infrared spectrum (Table 1) showed three absorption bands assignable to metal-nitrogen stretching frequencies and three bands assignable to metalchlorine stretching frequencies, and the complex therefore has been assigned the mer-configuration, although we are aware of the error which may arise when assignment of stereochemistry is based solely on solid-state infrared data (12).…”

Complexes of ruthenium(II) and ruthenium(III) with tertiary arsines

“…This is also supported by the ESR spectra, (at room temperature) which show a broad resonance signal with a 'g' value around 2.1. Assuming a meridional configuration (structure II) [12] for the complexes RuCI3(Ph2RAs)3 we suggest that the complexes We have also synthesised a series of dicarbonyl complexes of ruthenium(II) of stoichiometry RuX2(COh(Ph2RAsh (X = C1, Br; R = Pr, Bu) by the addition of the arsine to the pale yellow solution obtained by passing carbon monoxide through an alcoholic solution of ruthenium halide. These compounds are nonelectrolytes in nitrobenzene and show two vCO bands around 2000cm-' ( Table 2) and so should have configuration IV or V in analogy with the earlier findings [6].…”

Metal‐Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

“…Contributions from temperature independent paramagnetism (TIP) are well documented for 3 rd row complexes with d 4 (octahedral Re III , Os IV ) and d 6 configuration (square-planar, Os II ). 17 Single-crystal X-ray diffraction confirmed meridional coordination of the neutral diphosphinoamine ligand (Figure 1a). Complex 4 was investigated by cyclic voltammetry (CV) under argon.…”