Electrocatalytic reductive dimerization of the 2,2′-bipyridyl tungsten alkylidyne complex [W(CC6H4NMe2-4)(NCMe)(CO)2{κ2-2,2′-(NC5H4)2}]+

Duplessis, Elizabeth A.; Jelliss, Paul A.; Kirkpatrick, C. C.; Wampler, Keith M.

doi:10.1016/j.jorganchem.2006.07.029

Cited by 10 publications

(7 citation statements)

References 18 publications

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“…In general, these metal complexes are cationic and have ligand-based LUMOs. This is the case for the diazoalkane amido com- 3 ] + (various R and Ar), which dimerize at the diazoalkane C atom; [15] the salophen derivatives [MA C H T U N G T R E N N U N G (salophen)] n + (M = Ni, [16] Ti, [17] V, [17] Mn [18] ), which undergo a reversible dimerization at a ligand C atom; the 2,2'-bipyridine alkylidyne complex [W( CC 6 H 4 NMe 2 )(k 2 N 2 -bipy)A C H T U N G T R E N N U N G (NCMe)(CO) 2 ] + , which dimerizes at a bipy C atom; [19] and the carbene derivative [Cr-A C H T U N G T R E N N U N G (=CNEt 2 )(CO) 5 ] + , which dimerizes at the carbene carbon atom. [20] It has been reported that the reaction of the titanium complex trans-[TiCl 2 (k 2 N 2 -tmeda) 2 ] (tmeda = Me 2 NCH 2 CH 2 NMe 2 ) with acetonitrile leads to the reductive coupling of the latter, affording the dimetallic eneimido derivative trans-[Ti 2 Cl 4 {m-k 2 N 2 -NC(Me) = (Me)CN}(k 2 N 2tmeda) 2 ].…”

Section: Resultsmentioning

confidence: 99%

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Reductive Dimerization of Triruthenium Clusters Containing Cationic Aromatic N‐Heterocyclic Ligands

Cabeza¹,

Rı́o²,

Pérez‐Carreño³

et al. 2010

Chemistry A European J

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The cationic cluster complexes [Ru3(μ‐H)(μ‐κ2N,C‐L1 Me)(CO)10]+ (1+; HL1 Me=N‐methylpyrazinium), [Ru3(μ‐H)(μ‐κ2N,C‐L2 Me)(CO)10]+ (2+; HL2 Me=N‐methylquinoxalinium), and [Ru3(μ‐H)(μ‐κ2‐N,C‐L3 Me)(CO)10]+ (3+; HL3 Me=N‐methyl‐1,5‐naphthyridinium), which contain cationic N‐heterocyclic ligands, undergo one‐electron reduction processes to become short lived, ligand‐centered, trinuclear, radical species (1–3) that end in the formation of an intermolecular CC bond between the ligands of two such radicals, thus leading to neutral hexanuclear derivatives. These dimerization processes are selective, in the sense that they only occur through the exo face of the bridging ligands of trinuclear enantiomers of the same configuration, as they only afford hexanuclear dimers with rac structures (C2 symmetry). The following are the dimeric products that have been isolated by using cobaltocene as reducing agent: [Ru6(μ‐H)2{μ6‐κ4N2,C2‐(L1 Me)2}(CO)18] (5; from 1+), [Ru6(μ‐H)2{μ6‐κ4N2,C2‐(L2 Me)2}(CO)18] (6; from 2+), and [Ru6(μ‐H)2{μ4‐κ8N2,C6‐(L3 Me)2}(CO)18] (7; from 3+). The structures of the final hexanuclear products depend on the N‐heterocyclic ligand attached to the starting materials. Thus, although both trinuclear subunits of 5 and 6 are face‐capped by their bridging ligands, the coordination mode of the ligand of 5 is different from that of the ligand of 6. The trinuclear subunits of 7 are edge‐bridged by its bridging ligand. In the presence of moisture, the reduction of 3+ with cobaltocene also affords a trinuclear derivative, [Ru3(μ‐H)(μ‐κ2N,C‐L3′ Me)(CO)10] (8), whose bridging ligand (L3′ Me) results from the formal substitution of an oxygen atom for the hydrogen atom (as a proton) that in 3+ is attached to the C6 carbon atom of its heterocyclic ligand. The results have been rationalized with the help of electrochemical measurements and DFT calculations, which have also shed light on the nature of the odd‐electron species, 1–3, and on the regioselectivity of their dimerization processes. It seems that the sort of coupling reactions described herein requires cationic complexes with ligand‐based LUMOs.

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Section: Resultsmentioning

confidence: 99%

“…6·A C H T U N G T R E N N U N G (CH 2 Cl 2 ) 0.125 7·A C H T U N G T R E N N U N G (CH 2 Cl 2 ) 2 8·A C H T U N G T R E N N U N G (C 6 H 14 ) 0.5 formula C 19…”

Section: A C H T U N G T R E N N U N G [Bf 4 ]mentioning

confidence: 99%

Reductive Dimerization of Triruthenium Clusters Containing Cationic Aromatic N‐Heterocyclic Ligands

Cabeza¹,

Rı́o²,

Pérez‐Carreño³

et al. 2010

Chemistry A European J

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“…The solubility of these complexes (and of their proligands) is somewhat higher for the smallest systems, explaining the less-pronounced stripping peaks for 1 and 4 in CH 2 Cl 2 (the Supporting Information, Figure S2). [45] Complexa- . The latter are attributable to the coordinated bpy units.…”

Section: Full Papermentioning

confidence: 99%

“…This effect is attributable to the deposition of an electroactive layer on the glassy-carbon working electrode surface. [45] Complexa- Crystallography: Diffusion of diethyl ether vapour into a nitromethane solution of 1, and careful layering of hexane onto a CH 2 Cl 2 solution of 2 yielded crystals of apparently good quality. These unfortunately proved to be weakly diffracting, but nevertheless permitted unambiguous determination of the molecular structures (at 0.9 and 1.0 resolution for 1 and 2, respectively), packing arrangements and space groups.…”

Section: Full Papermentioning

confidence: 99%

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Coe

Foxon

Helliwell

et al. 2013

Chemistry A European J

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New complexes with six ferrocenyl (Fc) groups connected to ZnII or CdII tris(2,2′‐bipyridyl) cores are described. A thorough characterisation of their BPh4− salts includes two single‐crystal X‐ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(FeII)→π* metal‐to‐ligand charge‐transfer (MLCT) bands accompany the π→π* intraligand charge‐transfer absorptions in the near UV region. Each complex shows a single, fully reversible FeIII/II wave when probed electrochemically. Molecular quadratic nonlinear optical (NLO) responses are determined by using hyper‐Rayleigh scattering and Stark spectroscopy. The latter gives static first hyperpolarisabilities β0 reaching as high as approximately 10−27 esu and generally increasing with π‐conjugation extension. Z‐scan cubic NLO measurements reveal high two‐photon absorption cross‐sections σ2 of up to 5400 GM in one case. DFT calculations reproduce the π‐conjugation dependence of β0, and TD‐DFT predicts three transitions close in energy contributing to the MLCT bands. The lowest energy transition has octupolar character, whereas the other two are degenerate and dipolar in nature.

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“…Using the scheme of cyclic reduction and oxidation of heterocyclic derivatives in biological systems, the following mechanism of the participation of these ligands in the catalytic thiol oxidation can be suggested [36,43,44] (Scheme 3).…”

Section: Pyridine Complexesmentioning

confidence: 99%

Non-innocent ligands in copper complexes catalyzed oxidation of thiols

Gantman

Tarkhanova

Kolyagin

2016

Journal of Sulfur Chemistry

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Copper(II) chloride complexes with nitrogen-containing ligands (amines, amides, heterocycles) were studied as catalysts of selective oxidation of thiols to disulfides. This process has an important biochemical analogue -the formation of disulfide bridge in proteins [Wang C, Wesener SR, Zhang H, Cheng Y-Q. An FAD-dependent pyridine nucleotide-disulfide oxidoreductase is involved in disulfide bond formation in FK228 anticancer depsipeptide. Chem and Biol. 2009;16:585-593]; which affects their activity [Zhang L, Chou CP, Moo-Young M. Disulfide bond formation and its impact on the biological activity and stability of recombinant therapeutic proteins produced by Escherichia coli expression system. Biotech Adv. 2011;29:923-929]. Also, thiol oxidation is an important process of oil sweetening. The search for effective and stable catalysts for this reaction is still topical [Ganguly SK, Das G, Kumar S, Sain B, Garg MO. Mechanistic kinetics of catalytic oxidation of 1-butanethiol in light oil sweetening. Catal Tod. 2012;198:246-251]. This article describes a mechanistic study of thiol oxidation and non-innocent ligands transformations during this reaction. The studied ligands are capable of oxidizing thiols, the reaction being followed by reoxidation of the reduced forms of the ligands with air oxygen. The oxidative activity of the ligand correlates with catalyst activity for thiol oxidation. ARTICLE HISTORY

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Electrocatalytic reductive dimerization of the 2,2′-bipyridyl tungsten alkylidyne complex [W(CC6H4NMe2-4)(NCMe)(CO)2{κ2-2,2′-(NC5H4)2}]+

Cited by 10 publications

References 18 publications

Reductive Dimerization of Triruthenium Clusters Containing Cationic Aromatic N‐Heterocyclic Ligands

Reductive Dimerization of Triruthenium Clusters Containing Cationic Aromatic N‐Heterocyclic Ligands

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Non-innocent ligands in copper complexes catalyzed oxidation of thiols

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