Reactivity and coordination chemistry of aromatic carboxamide RC(O)NH[sub 2] and carboxylate ligands: Properties of pentaammineruthenium(II) and -(III) complexes

Chou, M H; Creutz, C; Sutin, N; Szalda, D J

doi:10.1021/ic00086a018

Title: Reactivity and coordination chemistry of aromatic carboxamide RC(O)NH[sub 2] and carboxylate ligands: Properties of pentaammineruthenium(II) and -(III) complexes

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Abstract

The pH dependences of the spectral and electrochemical properties of mononuclear carboxamido (NH[sub 3])[sub 5]RuNHC(O)R (R = Ph, 4-py-NH-Me[sup +], 4-py-N-H[sup +]) and carboxylato (NH[sub 3])[sub 5]RuOC(O)R (R = 4-py-N-Me[sup +]) complexes of Ru(II) and Ru(III) in aqueous solution have been examined. In contrast to the carboxylate complex (E[sub 1/2] = -0.053 V vs NHE), the deprotonated (-NHC(O)R[sup [minus]]) Ru[sup III/II] couples have rather negative reduction potentials, -0.25 (R = Ph), -0.23 (R = 4-py), and -0.13 (R = N-Me-4-py) V vs NHE, which are pH independent above the pK[sub a] of the Ru(II) complex (pH 4-8 depending upon R). In contrast, the carboxamido-Ru(III) complexes are weak bases, being protonated only in strongly acidic solutions (e.g. 5 M HClO[sub 4]). From the structural work (d(Ru(III)-amido N) for R = N-Me-4-py is 1.998(9) [angstrom]) and the behavior of the ligand-to-metal charge-transfer bands in carboxamido-Ru(III) complexes, considerable oxygen [pi]p-ruthenium(III) [pi]d bonding is inferred. Kinetic and equilibrium studies for the protonation of the Ru(II) amide and carboxylate complexes and for alkaline hydrolysis of the amide ligands is reported.

Authors:

Chou, M H; Creutz, C; Sutin, N; Szalda, D J ^[1]

Brookhaven National Lab., Upton, NY (United States)

Publication Date:: Wed Apr 13 00:00:00 EDT 1994

OSTI Identifier:: 7102240

Resource Type:: Journal Article

Journal Name:: Inorganic Chemistry; (United States)

Additional Journal Information:: Journal Volume: 33:8; Journal ID: ISSN 0020-1669

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMIDES; HYDROLYSIS; RUTHENIUM COMPLEXES; ELECTROCHEMISTRY; ABSORPTION SPECTROSCOPY; AROMATICS; CHEMICAL REACTIONS; PH VALUE; CHEMISTRY; COMPLEXES; DECOMPOSITION; LYSIS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; SOLVOLYSIS; SPECTROSCOPY; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats


                    Chou, M H, Creutz, C, Sutin, N, and Szalda, D J. Reactivity and coordination chemistry of aromatic carboxamide RC(O)NH[sub 2] and carboxylate ligands: Properties of pentaammineruthenium(II) and -(III) complexes.  United States: N. p., 1994. 
        Web.  doi:10.1021/ic00086a018.

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                    Chou, M H, Creutz, C, Sutin, N, & Szalda, D J. Reactivity and coordination chemistry of aromatic carboxamide RC(O)NH[sub 2] and carboxylate ligands: Properties of pentaammineruthenium(II) and -(III) complexes.  United States.  https://doi.org/10.1021/ic00086a018

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                    Chou, M H, Creutz, C, Sutin, N, and Szalda, D J. 1994.  
        "Reactivity and coordination chemistry of aromatic carboxamide RC(O)NH[sub 2] and carboxylate ligands: Properties of pentaammineruthenium(II) and -(III) complexes".  United States.  https://doi.org/10.1021/ic00086a018.

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@article{osti_7102240,

  title        = {Reactivity and coordination chemistry of aromatic carboxamide RC(O)NH[sub 2] and carboxylate ligands: Properties of pentaammineruthenium(II) and -(III) complexes},

  author       = {Chou, M H and Creutz, C and Sutin, N and Szalda, D J},

  abstractNote = {The pH dependences of the spectral and electrochemical properties of mononuclear carboxamido (NH[sub 3])[sub 5]RuNHC(O)R (R = Ph, 4-py-NH-Me[sup +], 4-py-N-H[sup +]) and carboxylato (NH[sub 3])[sub 5]RuOC(O)R (R = 4-py-N-Me[sup +]) complexes of Ru(II) and Ru(III) in aqueous solution have been examined. In contrast to the carboxylate complex (E[sub 1/2] = -0.053 V vs NHE), the deprotonated (-NHC(O)R[sup [minus]]) Ru[sup III/II] couples have rather negative reduction potentials, -0.25 (R = Ph), -0.23 (R = 4-py), and -0.13 (R = N-Me-4-py) V vs NHE, which are pH independent above the pK[sub a] of the Ru(II) complex (pH 4-8 depending upon R). In contrast, the carboxamido-Ru(III) complexes are weak bases, being protonated only in strongly acidic solutions (e.g. 5 M HClO[sub 4]). From the structural work (d(Ru(III)-amido N) for R = N-Me-4-py is 1.998(9) [angstrom]) and the behavior of the ligand-to-metal charge-transfer bands in carboxamido-Ru(III) complexes, considerable oxygen [pi]p-ruthenium(III) [pi]d bonding is inferred. Kinetic and equilibrium studies for the protonation of the Ru(II) amide and carboxylate complexes and for alkaline hydrolysis of the amide ligands is reported.},

  doi          = {10.1021/ic00086a018},

  url          = {https://www.osti.gov/biblio/7102240},
  journal      = {Inorganic Chemistry; (United States)},

  issn         = {0020-1669},

  number       = ,

  volume       = 33:8,

  place        = {United States},

  year         = {Wed Apr 13 00:00:00 EDT 1994},

  month        = {Wed Apr 13 00:00:00 EDT 1994}

}

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