Triosmium clusters compounds

Scheme 61. Synthesis of the silsesquioxane triosmium cluster compound 180.

The nature of the hydrogen bonding in methylated p-hydridodecacarbonyl-triosmium cluster compounds [68] and [69] has been investigated by... 

Reactions of triosmium clusters with organic compounds. K. Burgess, Polyhedron, 1984. 3, 1175... 

Metal carbonyl cluster compounds which contain three ruthenium or three osmium atoms in the cluster core are common.1 Potentially useful reagents for syntheses of these compounds are the triruthenium and triosmium dianions [M3(CO)h]2 (M = Ru, Os).2 Therefore, it is desirable to develop good synthetic routes to obtain [M3(CO)11]2- (M = Ru, Os) of high purity in high yields. A method that is particularly useful for generating [M3(CO)n]2 (M = Ru, Os) is the designed stoichiometric reduction of M3(CO)12 (M = Ru, Os) using an electron carrier such as potassium-benzophenone.3... 

Molecular rearrangements of diynes coordinated to triosmium carbonyl clusters have been reported.179 Triosmium clusters can act as templates for the rearrangement of l,4-dipyridylbuta-l,3-diyne, leading to the formation of fused-ring organic products, in a manner similar to that previously reported for other 1,3-diyne compounds. 

Triosmium clusters with electron counts of 46, 48, 49, 50, or 52 have been described (see Table I). The 49-electron system [Os3(CO)12] appears unique and has so far only been characterized by its esr spectrum (50). The 44-electron compound Os3(CO)10 has been considered as a reaction intermediate but without substantiating evidence (51). In established cases the varying... 

Transition metal complexes of other relevant organonitrogen compounds such as isoquinoline, 5,6-benzoquinoline, 7,8-benzoquinoline, acridine, and phenanthridine are also known, and they contain theN-ligand coordinated in either the p fN) or the tl -arene fashion [49, 69, 70]. The triosmium cluster Os3(CO),o(CH3CN)2 reacts with polyaromatic N-heterocycles such as 5,6-benzoquinoline and phenanthridine in an analogous manner to Py and Q, yielding J.3, n (N,C,C) complexes [69]. 

This section is dedicated to a description of the chemistries of trinithenium and triosmium clusters that do not contain hydrocarbon ligands. This section should be viewed as an addition to the chemistry described in sections 32.5 and 33 of COMC (1982) and section 12 of COMC (1995) as most of the main themes have been developed in the previous two decades. Overall, the interest in the cluster chemistry of ruthenium and osmium during the period 1994-2004 has tended to focus mainly on higher nuclearity and mixed metal clusters in order to enhance the developments in catalysis and bridge the gap between molecular clusters and nanoparricles. However, triruthenium and triosmium clusters continue to play a pivotal role in the chemistry of ruthenium and osmium. Both classes of clusters can be, and are, used extensively as precursors for the synthesis of higher nuclearity clusters as well as the formation of mono- and bimetallic complexes. No up-to-date review of the chemistry of either Ru3(CO)i2 or Os3(CO)i2 and their compounds is available, but several annual reviews of the chemistry of mthenium and osmium, which include the chemistry of the trinuclear clusters, are available. ... 

The rhodium complex [Rh(acac) (C2Hi )2] reacts with the unsaturated triosmium compound to give the 60-electron cluster species [Rh0s3(y-H)2(y-acac)(CO)10J (A7) in which the acac ligand acts as a five-electron donor, one oxygen atom bridging an Os — Rh separation of 3.292(2) so that the four metal atoms adopt a butterfly configuration. 

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