The chemistry of polynuclear compounds. Part 31. Synthesis of undecacarbonylhydridotriosmate(1–) and its reaction with octadeca-carbonylhexaosmium to give a carboxylate-bridged anionic enneaosmium species

Abstract

Treatment of [Os,(CO),,] with KOH in MeOH gives the anion [Os,H(CO),,]-; low-temperature 13C n.m.r. spectroscopy reveals that the structure of this hydrido-cluster is the same as that established for [Fe,H(CO),,]-in the solid state ; a t higher temperatures, fluxional behaviour similar to that previously observed for [Fe,H(CO),,]occurs. The [Os,H(CO),,]-anion reacts with [ O S ~( C O ) ~~] to produce the Os, anion [(OC),,,HOs,(~-CO,)-0s6(CO),,]-which contains an Os, and Os, unit linked by a CO, group. Carbon-73 n.m.r. spectroscopic studies reveal that the C atom of the C 0 2 linkage arises from the [OS,(CO)~~].

Transition Metal—Main Group Cluster Compounds

“…(54) Trimetallic frameworks support B3-cluster fragments in addition to the Bn-units (n = 1,2) described above. Ouster type 4 is exemplified by 1,2,3-(CpCo )3B3H5, (66)(67)(68) 1,2,3-(CpCo MIL 3 -C0)B 3 H 3 ( Figure 15a)(69,70) and 1,2,3-(CpCo )2Fe(CO)~3H3 (Figure 15b).…”

“…The type 81 and 82 clusters are quite well represented, although predominantly through compounds of osmium. By virtue of the molecular formula, OSS(CO)ISS may at first sight appear analogous to OSS(CO)ISC (216) but the extra two electrons which the sulfur atom provides for cluster bonding means that OSS(CO)ISS is a closo-octahedral cluster(402) while OSS(CO)ISC is a n ido-species with an interstitial carbon atom. The same applies to a comparison of the ruthenium systems RUS(CO)ISS (420) OsS(CO)ISS undergoes metal substitution to form 0s..(CO)12Pt(CO)(PPh3)S when treated with (Ph3P)2Pt(Cz~).…”

“…Returning to clusters of type 18, a variety of N-substituted clusters have been structurally characterized, for example, Fe3(CO~NSiMe3, (181) The cluster Fe3(CO~N2R2 is a type 21 molecule and its core structure is analogous to that in HRu3(CO~B2Hs (15,54) and the "parallel" isomer of toluene;…”

Studies on [Ru3(CO)12]-catalysed homogeneous transfer hydrogenation reactions; X-ray structure of [Ru4(CO)10Cl12(OPh)2]

“…After the catalytic reduction of benzylideneaniline ( w 40 turnovers), [Ru,H(CO),(PhNCPh)] (7) and the known mononuclear complex [Ru(CO),-(PhNcHC,H,),] (8) can be isolated from the reaction mixture through chromatographic techniques. We have earlier communicated the X-ray structure determination of (7). While (7) can also be obtained from the reaction of (1) with benzylideneaniline in refluxing hexane, ( 8) is formed only under the catalytic conditions, i.e.…”

“…Synthesis of complex (7). Benzylideneaniline (27 mg, 0.15 mmol) and complex (1) (64 mg, 0.1 mmol) in cyclohexane (30 cm3) were refluxed for 24 h. The resulting red-brown solution was subjected to column chromatography with hexane as the eluant.…”