Synthesis of the Five-Coordinate Ruthenium (II) Complexes [(PCP)Ru(CO)(L)][BAr'4] {PCP = 2,6-(CH2PtBu2)2 C6H3, BAr'4 = 3,5-(CF3)2C6H3, L= ɳ1-CICH2CI, ɳ 1-N2, or μ-Cl-Ru(PCP)(CO)}: Reactions with Phenyldiazomethane and Phenylacetylene

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Article discussing the synthesis of the five-coordinate ruthenium (II) complexes and reactions with phenyldiazomethane and phenylacetylene.

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12 p.

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Zhang, Jubo; Barakat, Khaldoon A.; Cundari, Thomas R., 1964-; Gunnoe, T. Brent; Boyle, Paul D.; Petersen, Jeffrey L. et al. October 6, 2005.

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Article discussing the synthesis of the five-coordinate ruthenium (II) complexes and reactions with phenyldiazomethane and phenylacetylene.

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12 p.

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Reprinted with permission from Inorganic Chemistry. Copyright 2005 American Chemical Society.

Abstract: Reaction of (PCP)Ru(CO)(CI) (1) with NaBAr'4 yields the bimetallic product [{(PCP)Ru(CO)}2 (μ-CI)][BAr'4] (2). The monomeric five-coordinate complexes [(PCP)Ru(CO)(ɳ1-CICH2CI)][BAr'4] (3) and [(PCP)Ru(CO)(ɳ1-N2)][BAr'4] (4) are synthesized upon reaction of (PCP)Ru(CO)(OTf) (6) with NaBAr'4 in CH2CI2 or C6H5F, respectively. The solid-state structures of 2,3, and 4 have been determined by X-ray diffraction studies of single crystals. The reaction of 3 with PhCHN2 or PhC=CH affords carbon-carbon coupling products involving the aryl group of the PCP ligand in transformations that likely proceed via the formation of Ru carbene or vinylidene intermediates. Density functional theory and hybrid quantum mechanics/molecular mechanics calculations were performed to investigate the bonding of weak bases to the 14-electron fragment [(PCP)Ru(CO)]+ and the energetics of different isomers of the product carbene and vinylidene complexes.

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  • Inorganic Chemistry, 2005, Washington D.C.: American Chemical Society, pp. 8379-8390

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  • Publication Title: Inorganic Chemistry
  • Volume: 44
  • Issue: 23
  • Page Start: 8379
  • Page End: 8390
  • Pages: 12
  • Peer Reviewed: Yes

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  • October 6, 2005

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  • Feb. 13, 2012, 2:23 p.m.

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  • Jan. 9, 2015, 5:11 p.m.

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Zhang, Jubo; Barakat, Khaldoon A.; Cundari, Thomas R., 1964-; Gunnoe, T. Brent; Boyle, Paul D.; Petersen, Jeffrey L. et al. Synthesis of the Five-Coordinate Ruthenium (II) Complexes [(PCP)Ru(CO)(L)][BAr'4] {PCP = 2,6-(CH2PtBu2)2 C6H3, BAr'4 = 3,5-(CF3)2C6H3, L= ɳ1-CICH2CI, ɳ 1-N2, or μ-Cl-Ru(PCP)(CO)}: Reactions with Phenyldiazomethane and Phenylacetylene, article, October 6, 2005; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc75424/: accessed April 29, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.