Stibine complexes

C. A. McAuliffe and W. Levason, Studies in Inorganic Chemistry, Vol. 1, Phosphine, Arsine and Stibine Complexes of the Transition Elements, Elsevier, Amsterdam, The Netherlands, 1979. 

Schiff base complexes, 37 265 selenocyanato complexes, 37 265 silyl complexes, 37 246-247 stibine complexes, 37 276 sulfato, chromato, and perrhenato complexes, 37 287... 

Reaction of Au(tht)Cl with SbMes3 resulted, regardless of the molar ratio used, in the isolation of the neutral complex Au(SbMes3)Cl 118, which also contains a linear Sb-Au-Cl system (Figure 4.32d), with the shortest Au-Sb bond [2.5100(2) A] found so far in gold-stibine complexes. For none of these complexes was further association of the molecules observed in the solid state. 

Distibines fall lowest in the spectrochemical series P2 > As2 > St>2,1529 a result which corresponds with the electronic spectra data for the monodentate series PEt3, AsEt3, SbEt3.1530 Mossbauer spectroscopy is a useful method for platinum stibine complexes. Coordination of the stibine causes a large increase in isomer shift and a decrease in quadrupole coupling constant in the 121Sb spectrum, as expected for the formation of a donor bond.1531... 

PHOSPHINE, ARSINE AND STIBINE COMPLEXES 51.9.2.1 Unidentate Ligands... 

All the compounds in Table II are soluble in aromatic solvents. They are all moderately air-sensitive, and the arsine and stibine complexes are thermally unstable, decomposing upon standing in solution—or more slowly in the solid state—to liberate nickel metal. 

There are now a substantial number of nitrido complexes of osmium(VI) and osmium(IV) as well as the osmiamate ion [OsVII 03N]. In addition to the ammine and ethylenediamine complexes, much recent work has been carried out on the bipy, phen and terpy complexes, often in connection with research into the photodissociation of water. The nitrosyl chemistry of the element, though seemingly not as extensive as that of ruthenium, has received much attention, and there has been considerable work on the phosphine, arsine and stibine complexes. 

As is the case with most elements the stibine chemistry has been a largely neglected area and this is certainly so for osmium very few osmium stibine complexes have been isolated. All of the species which have been isolated are with SbPh3, though oxidation states span the range II to IV. 

To some extent this situation has been rectified by a number of reviews of more limited range. Among these are the review by Robinson on the rhodium(II) carboxylates,19 and the reviews on the chemistry of [RhCl(PPh3)3]20 and [RhH(CO)(PPhj)3].21 The tertiary phosphine, arsine and stibine complexes of the element have also been covered in two reviews of these ligands complexes with the transition elements.22... 

There is an extensive chemistry of tertiary phosphine rhodium(III) complexes. However, there are comparatively few complexes of monodentate tertiary arsines, although the complexes of ditertiary arsines are more numerous. There are virtually no tertiary stibine complexes. The two main preparative routes to the complexes described in this section are (i) direct reaction pf the ligands with rhodium trichloride, which usually yields trichloro complexes and (ii) oxidative addition to rhodium(I) tertiary phosphine complexes, which gives rise to more diverse products of the type [RhXYZ(PRj) ], Metathetical reactions on the complexes prepared by either method (i) or (ii) have been used to prepare most of the remaining compounds. 

One interesting reaction undergone by the tri(styryl)arsine complexes is the bromination of the C=C bond by bromine in CC14 (equation 217).1013 Similar behavior970 is exhibited by the few tertiary stibine complexes (Table 75) that have been isolated. Few physical properties of these complexes have been investigated, but the 121 Sb Mossbauer parameters for both rhodium(III) complexes and the free ligands have been determined.1016... 

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