Formation of an Unsymmetrical Dinuclear Ruthenium Complex with μ‐H, μ‐OH, and μ‐κ2‐CO2 Bridges and Multiple Reactive Sites

Arikawa, Yasuhiro; Nagae, Shuichi; Morishita, Jun-ichi; Hiraki, Kei; Onishi, Masayoshi

doi:10.1002/ange.200501335

Cited by 4 publications

(2 citation statements)

References 31 publications

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“…, only one structure with the combination L = bpy and L 0 = 1,10phenanthroline has been reported (Gibson et al, 1998), although an analogue bearing both bpy and 2,2 0 :6 0 ,2 00 -terpyridine supporting ligands has also been described (Gibson et al, 1997). Meanwhile, the structure of a diruthenium complex with a metallacyclic CO 2 -bridged anion has been determined by Arikawa et al (2005).…”

Section: Database Surveymentioning

confidence: 99%

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO₂ ²⁻ bridge

2018

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Section: Database Surveymentioning

confidence: 99%

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO₂ ²⁻ bridge

2018

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“…Moreover, this type of dimetallacycles are very uncommon with only a few examples characterized crystallographically. [12] Nonetheless, dinuclear complexes with bridging CO 2 units in open arrangements, although scarce, have been reported previously. [13] The structural data of the CO 2 moiety indicate a partial p bond delocalization in the C À O bonds, with angles around the carbon (C35) close to 1208 and quite different C À O bond lengths for the free (C35-O7ffi1.24 ) and coordinated (C35-O8ffi1.35 ) oxygen atoms.…”

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Aerobic Oxidation of Carbon Monoxide in a Tetrametallic Complex

Tejel

Sancho

López

et al. 2012

Chemistry A European J

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Mapping the Transformation [{Ru^II(CO)₃Cl₂}₂]→[Ru^I₂(CO)₄]²⁺: Implications in Binuclear Water–Gas Shift Chemistry

Majumdar

Sinha

Ghatak

et al. 2010

Chemistry A European J

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The complete sequence of reactions in the base-promoted reduction of [{Ru(II)(CO)(3)Cl(2)}(2)] to [Ru(I) (2)(CO)(4)](2+) has been unraveled. Several mu-OH, mu:kappa(2)-CO(2)H-bridged diruthenium(II) complexes have been synthesized; they are the direct results of the nucleophilic activation of metal-coordinated carbonyls by hydroxides. The isolated compounds are [Ru(2)(CO)(4)(mu:kappa(2)-C,O-CO(2)H)(2)(mu-OH)(NP(F)-Am)(2)][PF(6)] (1; NP(F)-Am=2-amino-5,7-trifluoromethyl-1,8-naphthyridine) and [Ru(2)(CO)(4)(mu:kappa(2)-C,O-CO(2)H)(mu-OH)(NP-Me(2))(2)][BF(4)](2) (2), secured by the applications of naphthyridine derivatives. In the absence of any capping ligand, a tetranuclear complex [Ru(4)(CO)(8)(H(2)O)(2)(mu(3)-OH)(2)(mu:kappa(2)-C,O-CO(2)H)(4)][CF(3)SO(3)](2) (3) is isolated. The bridging hydroxido ligand in 1 is readily replaced by a pi-donor chlorido ligand, which results in [Ru(2)(CO)(4)(mu:kappa(2)-C,O-CO(2)H)(2)(mu-Cl)(NP-PhOMe)(2)][BF(4)] (4). The production of [Ru(2)(CO)(4)](2+) has been attributed to the thermally induced decarboxylation of a bis(hydroxycarbonyl)-diruthenium(II) complex to a dihydrido-diruthenium(II) species, followed by dinuclear reductive elimination of molecular hydrogen with the concomitant formation of the Ru(I)--Ru(I) single bond. This work was originally instituted to find a reliable synthetic protocol for the [Ru(2)(CO)(4)(CH(3)CN)(6)](2+) precursor. It is herein prescribed that at least four equivalents of base, complete removal of chlorido ligands by Tl(I) salts, and heating at reflux in acetonitrile for a period of four hours are the conditions for the optimal conversion. Premature quenching of the reaction resulted in the isolation of a trinuclear Ru(I) (2)Ru(II) complex [{Ru(NP-Am)(2)(CO)}{Ru(2)(NP-Am)(2)(CO)(2)(mu-CO)(2)}(mu(3):kappa(3)-C,O,O'-CO(2))][BF(4)](2) (6). These unprecedented diruthenium compounds are the dinuclear congeners of the water-gas shift (WGS) intermediates. The possibility of a dinuclear pathway eliminates the inherent contradiction of pH demands in the WGS catalytic cycle in an alkaline medium. A cooperative binuclear elimination could be a viable route for hydrogen production in WGS chemistry.

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Formation of an Unsymmetrical Dinuclear Ruthenium Complex with μ‐H, μ‐OH, and μ‐κ²‐CO₂ Bridges and Multiple Reactive Sites

Cited by 4 publications

References 31 publications

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO₂ ²⁻ bridge

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO₂ ²⁻ bridge

Aerobic Oxidation of Carbon Monoxide in a Tetrametallic Complex

Mapping the Transformation [{Ru^II(CO)₃Cl₂}₂]→[Ru^I₂(CO)₄]²⁺: Implications in Binuclear Water–Gas Shift Chemistry

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Formation of an Unsymmetrical Dinuclear Ruthenium Complex with μ‐H, μ‐OH, and μ‐κ2‐CO2 Bridges and Multiple Reactive Sites

Cited by 4 publications

References 31 publications

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO2 2− bridge

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO2 2− bridge

Aerobic Oxidation of Carbon Monoxide in a Tetrametallic Complex

Mapping the Transformation [{RuII(CO)3Cl2}2]→[RuI2(CO)4]2+: Implications in Binuclear Water–Gas Shift Chemistry

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Formation of an Unsymmetrical Dinuclear Ruthenium Complex with μ‐H, μ‐OH, and μ‐κ²‐CO₂ Bridges and Multiple Reactive Sites

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO₂ ²⁻ bridge

Crystal structure of a dinuclear ruthenium(II) complex with a bent CO₂ ²⁻ bridge

Mapping the Transformation [{Ru^II(CO)₃Cl₂}₂]→[Ru^I₂(CO)₄]²⁺: Implications in Binuclear Water–Gas Shift Chemistry