Osmium complexes dimers

Some interesting chemistry has appeared relating to the ability of the isocyanide ligand to stabilize unusual oxidation states. A series of palladium metal - metal bonded complexes has been synthesized by redox reactions involving two metal complexes in different formal oxidation states (33 -35). Similar ruthenium(I) and osmium(I) dimers have been prepared by an unusual homolytic fission of a ruthenium-carbon bond (36) or by singleelectron oxidation of Os(CNXylyl)5 (18). 

Only one example of an NHC-containing olefin metathesis catalyst containing a transition metal other than ruthenium has been reported in the literature. The NHC-osmium complexes 53a and 53b (Scheme 2) are synthesized from the dichloro(i]6-p-cymene)osmium dimer by addition of the NHC prepared in situ and abstraction of the chloride, followed by introduction of the ben-zylidene moiety with phenyl diazomethane. 

Imamura (11,20,21) synthesized several similar perpendicular dimers exploiting axial coordination of the 4-pyridyl free-base porphyrin to Ru(II)CO (3) and Os(II)CO (4) porphyrins (Fig. 1). The pyridine-ruthenium and pyridine-osmium interactions are much stronger than the pyridine-zinc interaction, and the complexes are perfectly stable in solution and can be isolated by precipitation. One of the ruthenium dimers was characterized by FAB-MS (11). Complexation is accompanied by characteristic changes in JH NMR chemical shift, indicating... 

Fig. 26. Bar charts relate the influence of different chelates in [Os(r 6-arene)Cl(XY)]n+ (XY = NJV- N,0- or 0,0-) on cytotoxicity, stability with respect to hydroxido-dimer formation, hydrolysis rates, and pKa of the aqua adduct for osmium-arene complexes. Shading indicates the range in observed values. Adapted from Ref. (III).

The tetranuclear osmium(VI) oxo imido complex [(Bu N)20s(/u-NBu )20s(NBu )(/u-0)]2 (2) is obtained as a side product in the reaction of [OSO4] with neat NHBu (SiMe3) (Scheme 1). Its structure can be described as a dimer of dimers with Cjh symmetry. ... 

A number of /.t-oxo-osmium(IV) porphyrin complexes have been prepared by aerial oxidation of [Os OEP)(CO)(MeOH)] in the presence 2,3-dimethylindole in CH2Cl2. " Cyclic voltammetric studies show that [0s2(0)(0EP)2(0Me)2] can undergo reduction to give an Os —O—Os dimer. The X-ray crystal structure of [0s(0EP)(0Me)]2( -0) shows a linear Os—O—Os backbone with Os—O and Os—OCH3 distances of 1.808 A and 1.997 A, respectively. 

Decene complexes with gold, 12 348 Deformation density, 27 29-33 Degradation reactions, heteronuclear gold cluster compounds, 39 336-337 Dehydration reactions, osmium(II), 37 351 Delocalization, see also Valence delocalization added electron, reduced dimer, 38 447, 449 optical centers, interaction with surroundings, 35 380 Density... 

---