Complexes of Osmium

Submitted by CHRISTOPHER L. GROSS, JULIA L. BRUMAGHEM, JESSE M. JEFFERIS, PAUL W. DICKINSON, and GREGORY S. GIROLAMI Checked by CHRISTOPHER W. GRIBBLE+ and T. DON TILLEY  

The chemistry of transition metal mono(cyclopentadienyl) molecules of the type (ri -C5R5)MX , where X is a halide ligand, has been widely explored. Such complexes can serve as catalysts or catalyst precursors for a wide variety of organic reactions ranging from the Ziegler-Natta polymerization of olefins to the 

Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801. Department of Chemistry, University of California at Berkeley, Berkeley, CA 94920. 

Except where noted, all procedures were carried out under a dry argon atmosphere using Schlenk and cannula techniques. Concentrated hydrobromic acid is 

The checkers used nitrogen instead of argon as an inert gas. 

---

Pyridazines form complexes with iodine, iodine monochloride, bromine, nickel(II) ethyl xanthate, iron carbonyls, iron carbonyl and triphenylphosphine, boron trihalides, silver salts, mercury(I) salts, iridium and ruthenium salts, chromium carbonyl and transition metals, and pentammine complexes of osmium(II) and osmium(III) (79ACS(A)125). Pyridazine N- oxide and its methyl and phenyl substituted derivatives form copper complexes (78TL1979). 

The carboxylates complexes of osmium have been studied less than the ruthenium analogues [173],... 

The pyridine complexes of osmium(III) result from reductive substitution... 

Bullitt, J. G. Cotton, F. A. (1971) The structure of a dinuclear complex of osmium(I) with a metal-to-metal single bond bis-(/i-acetatojhexacarbonyldiosmium, Inorg. Chim. Acta. 5, 406-412. 

Thus methyl and chalcoformaldehyde complexes of osmium are accessible by both electrophilic addition to a neutral d8 methylene complex and nucleophilic addition to a cationic d6 methylene complex. 

No sulfoxide complexes of osmium have been reported. Unsymmetri-cal dialkyl sulfoxides have been utilized in extraction studies, and methyl-4,8-dimethylnonyl sulfoxide has found application in the extraction of iron (266). Extraction of ruthenium from hydrochloric acid solutions by sulfoxides has been studied (470) and comparisons of sul-fones, sulfoxides, and thioethers as extractants for nitrosoruthenium species reported (441, 443). Similar studies on the extraction of nitro-soosmium species have been reported (442). 

Flowever, some associated materials might be perceived as toxic. For example, complexes of osmium find frequent use as electron mediators, because of their rich chemistry, stability, and redox activity. Osmium metal and most compounds are considered nontoxic, but the neat tetroxide of osmium is a strong oxidizer and is considered highly toxic in the U.S. and very toxic by the European Union. On the other hand, the aqueous solution, osmic acid, has been injected at 1% concentration in several European clinical trials, starting in the 1970s, for treatment of arthritis and hemophilia. - No toxic effects were observed. Thus, osmium toxicity might be a question not of in vivo chemistry, but of manufacture, where a concentrated form of the oxide might need to be handled. ... 

The complex (PPh4)[Os NC(CCl3)NCCl(CCl3) Cl5] may be regarded as an imido complex of osmium(VI), made by the reaction of OS2CI10 with trichloroacetonitrile and has been characterized by X-ray structural studies. The Os—N distance of 1.97 A is slightly shorter than that expected for a single bond. 

Of the Ru(IV) complexes recorded here most are mono-oxo species which, despite the strong axial distortion brought about by the terminal oxo ligand, are probably all paramagnetic. Semi-empirical molecular orbital calculations (INDO/1) for epoxidations effected by oxo-Ru(IV) complexes have been reported (a non-concerted [1 h- 2] pathway was preferred) [642], [643] and for alcohol oxidations by octahedral species containing an Ru" (0) unit [644]. The reactivity of high oxidation-state polypyridyl complexes of osmium and Ru, with particular emphasis on Ru(IV) and Os(IV) oxo species, has been reviewed [43]. 

The complete series, thio-, seleno-, and telluroformaldehyde complexes of osmium [OsCl(NO)(r72-E=CH2)(PPh3)2] (E = S, Se, Te), was obtained by reaction of the carbene complex [OsCl(NO)(=CH2)(PPh3)2] with elemental sulfur, selenium, and tellurium, respectively.53... 

Further variations on the theme have been achieved54 by anchoring species such as [RuivO-(terpy)(py)]2+ or complexes of osmium.55 Iron complexes have also been studied for example, evaporation of a solution containing [Fe(CN)5(H20)]3 and PVP on to an electrode will immobilize the pentacyanoferrate as a pyridyl complex, one in three available pyridyl groups being used to avoid precipitation prior to evaporation of solvent. 

Allyl hydride complexes of osmium are isolated from treatment of phosphine-substituted osmacyclobutane complex 114 with a thallium salt (Scheme 21). The reaction initially provides a mixture of an unstable -benzyl hydride complex 115 and the rf -allyl hydride complex 116 the -benzyl intermediate ultimately isomerizes to the latter complex, a very rare instance of isolable allylic hydride products generated from a starting metallacyclobutane <2004OM4858>. 

A high-yield general route to organotin complexes of osmium has been found... 

The first silylene complexes of osmium porphyrin, (TTP)Os=SiR2-THF, were prepared by treating K2[Os(TTP)] with Cl2SiR2 or the reaction of [Os(TTP)]2 with hexamethylsilacyclopropane (116). The molecular structure of (TTP)Os=SiEt2-2THF is stabilized by coordination of THF to the silicon, as shown by X-ray crystallography (Fig. 5). The measured Os—Si distance of 2.325(8) A is the shortest ever reported (116). 

Fig. 7. Formation and reactivity of base-stabilized terminal borylene complexes of osmium.

A new class of binuclear nitrido complexes of tetravalent osmium and ruthenium is described in which the metal atoms are symmetrically bridged by a nitride ligand to give a linear M-N—M unit They have the stoichiometries M2NX8(H20)2]3 and [M2N(NH3)8Y2]3+ (M = Os, Ru X = Cl, Br Y = Cl, Br, etc.). Studies are reported on their vibrational spectra, structures, and bonding. Preliminary studies are reported also on trinuclear complexes of osmium and iridium. Finally, the use of vibrational spectroscopy in the study of metal-nitrido and metal-oxo complexes is discussed briefly. 

---