31390-55-3Relevant academic research and scientific papers
Unsaturated triosmium carbonyl cluster complexes with bridging aryl ligands: Structures, bonding, and transformations
Adams, Richard D.,Rassolov, Vitaly,Zhang, Qiang
, p. 6368 - 6378 (2013/12/04)
Reactions of Os3(CO)10(NCMe)2, 1, with the series of aryl-gold complexes ArylAu(PPh3) [Aryl = phenyl = Ph, 2-naphthyl = 2-Np (2-C10H7) and 1-pyryl (1-C 16H10)] have provided the series of electronically unsaturated triosmium complexes Os3(CO)10(μ- η1-Ar)(μ-AuPPh3) [2, Ar = phenyl = Ph; 3, Ar = 2-naphthyl = 2-Np (2-C10H7); and Ar = 4 and 5, 2-pyryl and 4-pyryl], containing bridging η1-Ar ligands and a bridging Au(PPh3) group that bridges the same unsaturated Os-Os bond in the 46-electron cluster complex. All new compounds were characterized by single-crystal X-ray diffraction analyses. A DFT computational analysis of 2 has revealed that bonding of the bridging phenyl ligand to the metal atoms consists of a combination of delocalized σ-bonding between the ipso-carbon atom and the two proximate metal atoms and π-donation from the π-orbitals of the ring to those same metal atoms. There is no significant metal to ring π-back-bonding. Compound 3 exists as two isomers, 3a and 3b. Compound 3a contains a μ-η1-2-Np ligand. Compound 3b contains a μ-η2-2-Np ligand. The pyryl complexes 4 and 5 also exist as two isomers. These differ by the point of attachment of the η1-Ar ligand to the metal atoms. When heated to reflux in an octane solution (125 C), compounds 2, 3, 4, and 5 were decarbonylated and converted to the corresponding aryne complexes Os3(CO)9(μ3-Ar)(μ- AuPPh3)(μ-H), 6-9, which contain a triply bridging aryne ligand formed by the loss of one CO ligand from the complex and by a CH cleavage on the bridging Ar ligand. A mechanism for the transformation of 3b into the naphthyne complex 7 was established by DFT computational analyses.
Reactivity of [Os3(CO)10(NCMe)2] and [Os3(CO)10(μ-Cl)(μ-AuPPh3)] with 4-mercaptopyridine: X-ray structure of [Os3(CO)10(μ-H)(μ-SC5H 4N)] and [Os<
Sánchez-Cabrera, Gloria,Zuno-Cruz, Francisco J.,Ordó?ez-Flores, Berenice A.,Rosales-Hoz, María J.,Leyva, Marco A.
, p. 2138 - 2147 (2007/10/03)
The compound [Os3(CO)10(μ-Cl)(μ-AuPPh3)] (2) was prepared from the reaction between [Os3(CO)10(NCMe)2] (1) and [AuClPPh3] under mild conditions. The reaction of 2 with 4-mercapto
Reaction of (1-) with the (1+) Cation involving Insertion of an Os(CO)4 Fragment into the Gold-Phosphorus Bond
Cathey, Christopher,Lewis, Jack,Raithby, Paul R.,Ramirez de Arellano, M. Carmen
, p. 3331 - 3332 (2007/10/02)
The reaction of the cluster anion (1-) 1 with (1+) affords the cluster (μ-Cl)(CO)10> 2 which represents the first example in which an Os(CO)4 fragment has been inserted in to a gold-phosphine bond; the structure of 2 has been established by a single-crystal X-ray analysis.
