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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 712908.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Orthometalation of Dibenzo[1,2]quinoxaline with Ruthenium(II/III), Osmium(II/III/IV), and Rhodium(III) Ions and Orthometalated [RuNO](6/7) Derivatives
Authors:Maity, Suvendu; Kundu, Suman; Roy, Amit Saha; Weyhermüller, Thomas; Ghosh, Prasanta
Language:English
Date of Publication (YYYY-MM-DD):2015
Title of Journal:Inorganic Chemistry
Journal Abbrev.:Inorg. Chem.
Volume:54
Issue / Number:4
Start Page:1384
End Page:1394
Review Status:Internal review
Audience:Experts Only
Abstract / Description:A new family of organometallics of ruthenium(II/III), osmium(II/III/IV), and rhodium(III) ions isolated from CH activation reactions of dibenzo[1,2]quinoxaline (DBQ) using triphenylphosphine, carbonyl, and halides as coligands is reported. The CN-chelate complexes isolated are trans-[Ru-III(DBQ)(PPh3)2Cl2] (<bold>1</bold>), trans-[Ru-II(DBQ)(CO)(PPh3)2Cl] (<bold>2</bold>), trans-[Os-III(DBQ)(PPh3)(2)Br-2] (<bold>3</bold>), trans-[Os-II(DBQ)(PPh3)(2)(CO)Br] (<bold>4</bold>), and trans-[Rh-III(DBQ)(PPh3)2Cl2] (<bold>5</bold>). Reaction of <bold>1</bold> with NO affords trans-[Ru(DBQ)(NO)(PPh3)(2)Cl]Cl (<bold>6(</bold>+)Cl), isoelectronic to <bold>2</bold>, with a byproduct, [Ru(NO)(PPh3)2Cl3] (<bold>7</bold>). Complexes <bold>15</bold> and <bold>6(</bold>+) were characterized by elemental analyses, mass, IR, NMR, and electron paramagnetic resonance (EPR) spectra including the single-crystal X-ray structure determinations of <bold>13</bold> and <bold>5</bold>. The Ru-III-C, Ru-II-C, Os-III-C, and Rh-III-C lengths are 2.049(2), 2.074(3), 2.105(16), and 2.012(3) angstrom in <bold>1</bold>, <bold>2</bold>, <bold>3</bold>, and <bold>5</bold>. In cyclic voltammetry, <bold>2</bold>, <bold>3</bold>, and <bold>4</bold> undergo oxidation at 0.59, 0.39, and 0.46 V, versus Fc(+)/Fc couple, to trans-[Ru-III(DBQ)(CO)(PPh3)2Cl](+) (<bold>2</bold>+), trans-[OsIV(DBQ)(PPh3)(2)Br-2](+) (<bold>3</bold>+), and trans-[Os-III(DBQ)(CO)(PPh3)2Br](+) (<bold>4</bold>+) ions. Complex <bold>3</bold>+ incorporates an OsIV(d4 ion)C bond. The <bold>6(</bold>+)/trans-[Ru(DBQ)(NO)(PPh3)(2)Cl] (<bold>6</bold>) reduction couple at -0.65 V is reversible. <bold>2(</bold>+), <bold>3(</bold>+), <bold>4(</bold>+) and <bold>6</bold> were substantiated by spectroelectrochemical measurements, EPR spectra, and density functional theory (DFT) and time-dependent (TD) DFT calculations. The frozen-glass EPR spectrum of the electrogenerated <bold>6</bold> exhibits hyperfine couplings due to 99,101Ru and N-14 nuclei. DFT calculations on trans-[Os-III(DBQ)(PMe3)(2)Br-2] (<bold>3(</bold>Me)), S-t = 1/2 and trans-[Os-IV(DBQ)(PMe3)(2)Br-2](+) (<bold>3(</bold>Me+)), S-t = 0, trans-[Ru(DBQ)(NO)(PMe3)(2)Cl](+) (<bold>6(</bold>Me+)), S-t = 0 and trans-[Ru(DBQ)(NO)(PMe3)(2)Cl] (<bold>6(</bold>Me)), S-t = 1/2, authenticated a significant mixing between dOs and paromatic* orbitals, which stabilizes (MC)-C-II/III/IV bonds and the [RuNO](6) and [RuNO](7) states, respectively, in <bold>6(</bold>+) and <bold>6</bold>, which is defined as a hybrid state of trans-[Ru-II(DBQ)(NO<bold>)(PPh</bold>3)(2)Cl] and trans-[Ru-I(DBQ)(NO+)(PPh3)(2)Cl] states.
Comment of the Author/Creator:Date: 2015, FEB 16 2015
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:[Maity,S.; Kundu,S.; Roy,A.S.; Ghosh,P. ] RK Miss.Residential Coll., Dept.Che. Kolkata 103, India.
Identifiers:ISI:000349656600028 [ID No:1]
ISSN:0020-1669 [ID No:2]
DOI:10.1021/ic502320m [ID No:3]
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