1238313-72-8Relevant academic research and scientific papers
Facile cleavage of phenyl groups from BiPh3 in its reactions with Os3(CO)10(NCMe)2 and evidence for localization of π-bonding in a bridging benzyne ligand
Adams, Richard D.,Kan, Yuwei,Zhang, Qiang
, p. 475 - 481 (2014)
Three new compounds were obtained from the reaction of Os 3(CO)10(NCMe)2, 1 with BiPh3 in a methylene chloride solution at reflux. These have been identified as Os 3(CO)10(μ3-C6H4), 3, Os3(CO)10Ph(μ-η2- O=CPh), 4, and HOs6(CO)20(μ-η2-C6H 4)(μ4-Bi), 6. Two other products Os2(CO) 8(μ-BiPh), 2, and HOs5(CO)18(μ- η2-C6H4)(μ4-Bi), 5 were obtained previously from the reaction of Os3(CO)11(NCMe) with BiPh3. Cleavage of the phenyl groups from the BiPh3 was the dominant reaction pathway and two of the products 3 and 4 contain rings but no bismuth. Each of the new compounds was characterized structurally by single-crystal X-ray diffraction methods. Compound 3 contains a triply-bridging benzyne (C6H4) ligand that exhibits a pattern of alternating long and short CeC bonds that can be attributed to partial localization of the π-bonding in the C6 ring. The localization in the π-bonding in the ring is supported by DFT calculations. Compound 4 contains a triangular cluster of three osmium atoms with a bridging benzoyl ligand and a terminally coordinated phenyl ligand. Compound 6 contains six osmium atoms divided into two groups of four and two and the two groups are linked by a spiro-bridging bismuth atom. The group of two osmium atoms contains a bridging C6H4 ligand. When heated, compound 4 was converted into 3 and the compound Os3(CO)10(μ- η2-O=CPh)2, 7. Compound 7 contains two bridging benzoyl ligands.
Osmium-bismuth complexes from the reaction of Os3(CO) 11(NCMe) with BiPh3
Adams, Richard D.,Pearl, William C.
, p. 7170 - 7175 (2010/09/16)
Five new compounds were obtained from the reaction of Os 3(CO)11(NCMe), 1, with BiPh3 in hexane solution at reflux. These have been identified as Os2(CO)8(μ- BiPh), 2, Os(CO)4Ph2, 3, Os4(CO) 14(μ-η3-O - CC6H5) (μ4-Bi), 4, Os4(CO)15Ph(μ4-Bi) , 5, and Os5(CO)19Ph(μ4-Bi), 6. Cleavage of the phenyl groups from the BiPh3 was the dominant reaction pathway. Fragmentation of the original triosmium cluster was accompanied by reaggregation processes that were facilitated by the naked bismuth to yield the higher nuclearity osmium cluster complexes containing spiro-bridging bismuth ligands. Compound 6 was photo-decarbonylated to yield the compound HOs 5(CO)18(μ-η2-C6H 4)(μ4-Bi), 7, formed by ortho-CH activation of the σ-bonded phenyl ring in 6 to form a bridging η2-benzyne ligand. Compounds 2- 7 were each characterized structurally by a single-crystal X-ray diffraction analysis.
