Coordination Chemistry of 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane: Preparation and Characterization of Ru(II) Complexes

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Article discussing preparation and characterization of Ru(II) complexes.

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11 p.: ill.

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Joslin, Evan E.; McMullin, Claire L.; Gunnoe, T. Brent; Cundari, Thomas R., 1964-; Sabat, Michal & Myers, William H. March 27, 2012.

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Article discussing preparation and characterization of Ru(II) complexes.

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11 p.: ill.

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Reprinted with permission from the Inorganic Chemistry journal. Copyright 2012 American Chemical Society.

Abstract: The complexes TpRu[P(OCH₂)₂(OCCH₃]-(PPh₃)Cl (2) [Tp = hydridotris(pyrazolyl)borate; P- (OCH₂)₂(OCCH₃) (1) = (4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane] and TpRu(L)(PPh₃) CL [L = P(OCH₂)₃CEt (3), PMe₃ (4) or P(OMe)₃ (5)], (η⁶-C₆H₆)Ru(L)Cl₂ {L = PPh₃ (6), P(OMe)₃ (7), PMe₃ (8), P(OCH₂)₃CEt (9), CO (10) or P(OCH₂)₂(OCCH₃) (11)] and (η⁶-p-cymene)Ru(L)Cl₂ [L = P(OCH₂)₃CEt (12), P(OCH₂)₂(OCCH₃)P(OCH₂)₂(OCCH₃) (13), P(OMe)₃ (14) or PPh₃ (15)] have been synthesized, isolated, and characterized by NMR spectroscopy, cyclic voltammetry, mass spectrometry, and, for some complexes, single crystal X-ray diffraction. Data from cyclic voltammetry and solid-state structures have been used to compare the properties of (1) with other phosphorous-based ligands as well as carbon monoxide. Data from the solid-state structures of Ru (II) complexes show that P(OCH₂)₂(OCCH₃) has a cone angle of 104. Cyclic voltammetry data reveal that the Ru(II) complexes bearing P(OCH₂)₂(OCCH₃) have more positive Ru(III/II) redox potentials than analogous complexes with the other phosphorous ligands; however, the Ru(III/II) potential for (η⁶-C₆H₆)Ru(CO)Cl₂. For the Ru(II) complexes studied herein, these data are consistent with the overall donor ability of I being less than other common phosphines (e.g., PMe₃ or PPh₃) or phosphites [e.g., P(OCH₂)₃CEt or P(OMe)₃] but greater than carbon monoxide.

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  • Inorganic Chemistry, 2012, Washington DC: American Chemical Society, pp. 4791-4801

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  • Publication Title: Inorganic Chemistry
  • Volume: 51
  • Issue: 8
  • Page Start: 4791
  • Page End: 4801
  • Peer Reviewed: Yes

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  • March 27, 2012

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  • Aug. 23, 2013, 9:48 a.m.

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Joslin, Evan E.; McMullin, Claire L.; Gunnoe, T. Brent; Cundari, Thomas R., 1964-; Sabat, Michal & Myers, William H. Coordination Chemistry of 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane: Preparation and Characterization of Ru(II) Complexes, article, March 27, 2012; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc177426/: accessed May 26, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.