Stibine complexes, osmium

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. 

Considerable structural information is available on osmium complexes of tertiary phosphines, arsines and stibines (Table 1.13) [152, 157]. 

Considerable structural information is available on osmium complexes of tertiary phosphines, arsines and stibines (Table 1.13) [152, 157], Comparison with data (mainly obtained from EXAFS measurements) on osmium diarsine complexes (Table 1.14) shows that as the oxidation state increases, osmium-halogen bonds shorten whereas Os-P and Os-As bonds lengthen. Bond shortening is predicted for bonds with ionic character,... 

It is a singular circumstance that the known chemistry of the tertiary phosphite complexes of osmium differs quite significantly from that of the tertiary phosphines, arsines and stibines. The closest analogue to P(OR)3 in osmium coordination chemistry would seem to be PF3, but even here the similarities are not marked. The oxidation states found are 0, II, III and IV (there are no established zerovalent unsubstituted osmium phosphine complexes), and the phosphites form unsubstituted species of the type OsL and [OsL ] " which have no counterparts in phosphine chemistry. The reason for these differences must be associated in part at least with the different cone angles and basicities of P(OR)3 ligands as against PR3. Further similarities and differences between the chemistries of osmium phosphines, phosphites and phosphorus trihalide complexes would obviously constitute a worthwhile study. 

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