Electrocatalytic oxidation by binuclear ruthenium complexes incorporating the anionic tripod ligand [(.eta.5-C5H5)Co{(CH3O)2P:O}3]-

Kelson, Eric P.; Henling, Lawrence M.; Schaefer, William P.; Labinger, Jay A.; Bercaw, John E.

doi:10.1021/ic00065a012

Cited by 27 publications

(22 citation statements)

References 1 publication

(13 reference statements)

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“…The Ru–O–Ru angles were less than 90° (77.80(15)–78.44 (15)°), and the O–Ru–O angles were around 100° (101.65(11)–101.94(17)°) to form the diamond core, and the Ru–O–Ru angles of [ 2 Cl ] + and [ 2′ Cl ] + were closer to 180°. The structural parameters of the {Ru 2 (μ-O) 2 } core of [ 3 L ] 2+ were similar to those of a previously reported Ru III –Ru IV complex having the {Ru 2 (μ-O) 2 } core, [{Ru III,IV (dtne)} 2 (μ-O) 2 (μ-O 2 CO)]PF 6 (dtne; 1,2-bis(1,4,7-triazacyclononan-1-yl)ethane), but the Ru–O(bridge) lengths (1.912(7)–1.939(5) Å) were shorter than those of doubly hydroxido-bridged complexes of Ru III –Ru III , [{Ru III,III (tacn)} 2 (μ-OH) 2 (μ-O 2 CO)]Br 2 (tacn; 1,4,7-triazacyclononane), [{Ru III,III (tacn)} 2 (μ-OH) 2 (μ-O 2 CCH 3 )]I 3 , [{Ru III,III Cl(tacn)} 2 (μ-OH) 2 ](BPh 4 ) 2 , or [{Ru III,III L OMe } 2 (μ-OH) 2 (μ-O 2 CH)]CF 3 SO 3 (L oMe ; [(η 5 -C 5 H 5 )Co{(CH 3 O) 2 P = O} 3 ] − ) (1.985(3)–2.052(7) Å). As the electronic structure of [ 3 L ](PF 6 ) 2 was in the Ru III –Ru IV mixed-valent state, the Ru centers strongly bonded to the oxido ligands than the Ru III –Ru III ones.…”

Section: Resultssupporting

confidence: 82%

“…In case of [3H + CH 3 COO ] 3+ , bridging oxido and hydroxido ligands and an oxygen of the acetato occupied the remaining three coordination sites of a ruthenium center. 15 but the Ru−O(bridge) lengths (1.912(7)−1.939(5) Å) were shorter than those of doubly hydroxido-bridged complexes of Ru III −Ru III , [{Ru III,III (tacn)} 2 (μ-OH) 2 (μ-O 2 CO)]Br 2 (tacn; 1,4,7-triazacyclononane), 15 [{Ru III,III (tacn)} 2 (μ-OH) 2 (μ-O 2 CCH 3 )]I 3 , 16 [{Ru III,III Cl(tacn)} 2 (μ-OH) 2 ](BPh 4 ) 2 , 17 or [{Ru III,III L OMe } 2 (μ-OH) 2 (μ-O 2 CH)]CF 3 SO 3 (L oMe ; [(η 5 -C 5 H 5 )Co{(CH 3 O) 2 P = O} 3 ] − ) 18 (1.985(3)−2.052(7) Å). As the electronic structure of [3 L ](PF 6 ) 2 was in the Ru III −Ru IV mixed-valent state, the Ru centers strongly bonded to the oxido ligands than the Ru III − Ru III ones.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes

et al. 2019

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Syntheses, properties, and reactions of hydroxido-or oxido-bridged dinuclear ruthenium complexes bearing a tridentate auxiliary ligand, ethylbis(2-pyridylmethyl)amine (ebpma) or benzylbis(2-pyridylmethyl)amine (bbpma), have been investigated. Reduction reactions of a singly oxidob r i d g e d d i r u t h e n i u m c o m p l e x b e a r i n g e b p m a , [{Ru III,IV Cl 2 (ebpma)} 2 (μ-O)] + ([2 Cl ] + ), by zinc in acetonitrile afforded an acetonitrile-substituted singly oxido-bridged complex in the Ru III −Ru III isovalent state, [{Ru III,III Cl(NCCH 3 )(ebpma)} 2 (μ-O)] 2+ ([2 CH 3 CN ] 2+ ). Chlorido ligand abstraction reactions using silver salts have also been attempted. Through a reaction of [2 Cl ] + with two equimolar amounts of AgNO 3 in water−acetone, a singly oxido-bridged complex having an aqua and a hydroxido, [{Ru III Cl(OH 2 )(ebpma)}(μ-O){Ru IV Cl-(OH)(ebpma)}] 2+ ([2 H 2 O-OH ] 2+ ), was obtained. Reactions with four equimolar amounts of AgL (L = CH 3 COO − or NO 3 − ) in water−acetone gave doubly oxido-and bidentate oxygen donor ligand-bridged diruthenium complexes of Ru(III)−Ru(IV), [{Ru III,IV (ebpma)} 2 (μ-O) 2 (μ-L)] 2+ ([3 L ] 2+ ; L = O 2 CCH 3 ; [3 CH 3 COO ] 2+ , L = O 2 NO; [3 NO 3 ] 2+ ). Reactions of [3 L ] 2+ under acidic conditions afforded a corresponding one-protonated species having the {Ru 2 (μ-O)(μ-OH)} core. Reactivity and electronic structure of the oxido-bridged diruthenium complexes were studied by electrochemical, spectroscopic, and theoretical methods.

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Section: Resultssupporting

confidence: 82%

Section: ■ Results and Discussionmentioning

confidence: 99%

Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes

et al. 2019

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“…[16][17][18][19][20][21][22][23] Single-bonded Ru(III)-Ru(III) dimers containing other bridging ligands (RCO 2 -, OH -, and dppm/Cl -) have been reported. [24][25][26] Experimental Details General Information. All reagents were purchased from Aldrich and used without further purification.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H₂edta)(μ-SC₆H₅)]₂

et al. 2000

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“…Like Cp and Tp ligands, π-donating L OR - ligands exhibit rich organometallic − and catalytic − chemistry. Recently, chiral Tp ligands have been synthesized and used for asymmetric cyclopropanation of olefins. , This prompted us to develop a chiral version of Kläui's tripodal ligands that form stable complexes with a wide range of metal ions .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Crystal Structure of a ChiralC₃-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis

et al. 2004

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Treatment of Na[P(O)(S-BINOL)] (S-BINOL = (S)-(−)-bi-2-naphthol) with [CpCo(CO)I2] afforded the chiral C 3-symmetric oxygen tripodal ligand Na[Co{P(O)(S-BINOL)}3] (Na(1)). Recrystallization of Na(1) from acetone/toluene yielded Na(1)(C6H12O2)2 (C6H12O2 = diacetone alcohol), which has been characterized by X-ray diffraction. The solid-state structure of Na(1)(C6H12O2)2 features a six-coordinated Na with one η2 and one η1 diacetone alcohol ligand. Treatment of Na(1) with [(η6-p-cymene)RuCl2]2, [Ru(CO)Cl(CHCHPh)(PPh3)3], and [Pr(OTf)3] (OTf = triflate) afforded [(η6-p-cymene)Ru(1)][PF6] (3), [Ru(1)(CO)(CHCHPh)(PPh3)] (4), and [Pr(1)2(OTf)] (5), respectively. Treatment of Na(1) with [Cu(MeCN)4][BF4] in the presence of PhC⋮CH and Me3SiC⋮CSiMe3 afforded [Cu(1)(η2-PhC⋮CH)] (6) and [Cu(1)(η2-Me3SiC⋮CSiMe3)] (7), respectively, which have been characterized by X-ray diffraction. In both 6 and 7, the Cu atom exhibits a distorted 2 + 1 tripod ligand coordination with one Cu−O bond significantly longer than the other two. Na(1) has been employed for the Cu-catalyzed enantioselective aziridination of styrene, the Ti-catalyzed azidolysis of cyclohexene oxide, and the allylation of benzaldehyde with allyltrichlorosilane.

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Electrocatalytic oxidation by binuclear ruthenium complexes incorporating the anionic tripod ligand [(.eta.5-C5H5)Co{(CH3O)2P:O}3]-

Cited by 27 publications

References 1 publication

Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes

Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes

Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H₂edta)(μ-SC₆H₅)]₂

Synthesis and Crystal Structure of a ChiralC₃-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis

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Electrocatalytic oxidation by binuclear ruthenium complexes incorporating the anionic tripod ligand [(.eta.5-C5H5)Co{(CH3O)2P:O}3]-

Cited by 27 publications

References 1 publication

Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes

Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes

Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H2edta)(μ-SC6H5)]2

Synthesis and Crystal Structure of a ChiralC3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis

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Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H₂edta)(μ-SC₆H₅)]₂

Synthesis and Crystal Structure of a ChiralC₃-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis