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Abstract
The synthesis of cyclometalated osmium complexes is usually more complicated than of other transition metals such as Ni, Pd, Pt, Rh, where cyclometalation reactions readily occur via direct activation of C–H bonds. It differs also from their ruthenium analogs. Cyclometalation for osmium usually occurs under more severe conditions, in polar solvents, using specific precursors, stronger acids, or bases. Such requirements expand reaction mechanisms to electrophilic activation, transmetalation, and oxidative addition, often involving C–H bond activations. Osmacycles exhibit specific applications in homogeneous catalysis, photophysics, bioelectrocatalysis and are studied as anticancer agents. This review describes major synthetic pathways to osmacycles and related compounds and discusses their practical applications.
Highlights
Osmium is the heaviest and rarest stable element in the earth’s crust, with a concentration of approximately 0.05 part per billion
Osmium chemistry is not limited to its oxides, and numerous coordination, organometallic, and cluster compounds have been prepared, though their chemistry is not as deeply explored as that of ruthenium [4]
Some osmium compounds were compiled in Gmelin Handbuch der Anorganischen Chemie in the 1980s [6]
Summary
Osmium is the heaviest and rarest stable element in the earth’s crust, with a concentration of approximately 0.05 part per billion. Clark et al studied by X-ray crystallography four cyclometalated osmium complexes (51–55) obtained via the transmetalation reaction between hydride precursors [OsH(Cl)(CO)(PPh3)3] and organomercurial derivatives of 2-phenylpyridine. -heterocycle and in 3-position by a phenoxy group afford corresponding cyclometalated complexes (72, 73) This reaction is associated with the metal-mediated degradation of the ligand which involves two C−H bond activations and a parallel C−N and C−C rupture within the four-membered rings [60,61] (Table 2). The phenyl triazine ligand forms pincer complex but can a erate a dinuclear bis-cyclometalated osmium complex (Figure 17) [68]. The phenyl triazine ligand forms pincer complex but can generate a dinuclear bis-cyclometalated osmium complex (Figure 17) [68].
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