Carbonyl complexes of manganese, rhenium and molybdenum with 2-pyridylimino acid ligands

Martín‐Alvarez, José M.; García‐Rodríguez, Raúl; Miguel, Daniel

doi:10.1016/j.jorganchem.2007.09.025

Cited by 40 publications

(17 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…This behavior is similar to that reported for the symmetric non-aromatic Mn R-DAB (R = alkyl) compounds. 8,30 The formation of a stable bicarbonate complex, either through the coordination to the metal center or via the imino C=N bond 23,37 leads to the need of increased overpotential. From that point of view, the steric hindering (protection) of the metal center/the imino C=N bond in the Mn(IP) complexes is advantageous as it disfavors the Mn Mn dimerization (when comparing MnIMP with MnDIPIMP).…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO₂ Reduction

et al. 2016

View full text Add to dashboard Cite

Manganese tricarbonyl bromide complexes incorporating IP (2-[(phenylimino)]pyridine) derivatives, [MnBr(CO) 3 (IP)], are demonstrated as a new group of catalysts for CO 2 reduction, which represent the first example of utilization of phenylimino pyridine ligands on manganese centers for this purpose. The key feature is the asymmetric structure of the redox non-innocent ligand that permits independent tuning of its steric and electronic properties. The -diimine ligands and five new Mn(I) compounds have been synthesized, isolated in high yields and fully characterized, including X-ray crystallography. Their electrochemical and electrocatalytic behavior was investigated using cyclic voltammetry and UV-vis /IR spectroelectrochemistry within an OTTLE cell. Mechanistic investigations under an inert atmosphere have revealed differences in the nature of the reduction products as a function of steric bulk of the ligand. The direct ECE (electrochemical-chemical-electrochemical) formation of a five-coordinate anion [Mn(CO) 3 (IP)] -, a product of 2-electron reduction of the parent complex, is observed in case of the bulky The interest in solar fuels in terms of both photocatalytic and electrocatalytic CO 2 reduction 1 , in the latter case utilizing sustainable electricity, has been increasing markedly in the new millennium. The recent demonstration of the electrocatalytic activity of manganese 2 analogues of the archetypal Re(I) catalysts 3,4,5,6 for CO 2 reduction has given a new impetus to research into noble-metal-free catalytic systems. [MnBr(CO) 3 ( -diimine)] complexes have been shown to outperform rhenium-based analogues with regard to CO 2 reduction under certain conditions. 7 Most notably, the presence of a Brönsted acid 7-10 appears to be a prerequisite for catalysis with a range of tricarbonyl Mndiimine complexes. Mechanistic studies 5,10 of the active 2,2 -bipyridine-based (Rbpy) manganese catalysts have shown that one-electron reduction of the parent complex [MnBr(CO) 3 (R-bpy)] precursor results in the formation of the Mn Mn dimer [Mn(CO) 3 (Rbpy)] 2 . 8,9 Notably, neither the primary reduction product [MnBr(CO) 3 (R-bpy )] nor the five-coordinate radical intermediates [Mn(CO) 3 (R-bpy)] have been detected by either UV-vis or IR spectroscopy. 2,7 Nanosecond time-resolved infrared (TRIR) studies reveal that no detectable solvent adduct is formed before the dimerization of Mn species on this timescale; instead, the five-coordinate species is observed, which rapidly dimerises. 10 For some of the Re analogues, a one-electron reduced complex, [ReCl(CO) 3 (R-bpy )] was observed by IR spectroscopy and identified by the ca. 15-20 cm -1 decrease in the (CO) energy, 11,12,13 as was the five-coordinate radical [Re(CO) 3 ( t Bubpy)] by an additional 15-20 cm -1 shift .Two mechanisms have been proposed 10,14-18 for the ultimate reduction of [Mn(CO) 3 ( -diimine)] 2 in the presence of CO 2 , which can be referred to as the anionic, and the oxidative addition 19 pathways. The anionic pathway involves reduction of ...

show abstract

Section: Discussionmentioning

confidence: 99%

“…0.7 V is needed to reduce the bicarbonate complex, resulting in the recovery of the five-coordinate anion that triggers the catalytic conversion of CO 2 . 37 forms the carbonate complex in two 1e-reduction steps, via a direct coordination to the Re center, without C=N being directly involved.…”

Section: Ir and Uv-vis Spectroelectrochemistry Under Co 2 Atmospherementioning

confidence: 99%

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO₂ Reduction

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Transition metal complexes containing ancillary ligands, pyridyl-imines and N-substituted 2-iminoalkylpyridines have been applied for synthetic, spectroscopic and kinetic studies, [1][2][3][4][5][6][7][8][9][10] photoluminescence and photochemistry, 11 as catalysts for organic transformation, [12][13][14][15][16][17][18] electrochemistry, [19][20][21] bioinorganic chemistry, 22,23 supramolecular chemistry, 24,25 molecular magnetism [26][27][28][29] and olefin polymerisation. [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] In contrast, poly(methylmethacrylate) (PMMA) is a universal polymer with optical applications.…”

Section: Introductionmentioning

confidence: 99%

Cd(II) and Zn(II) Complexes Containing N,N'-Bidentate N-(Pyridin-2-ylmethylene)cyclopentanamine: Synthesis, Characterisation and Methyl Methacrylate Polymerisation

Song¹,

Kim²,

Lee³

et al. 2014

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

The reaction between [CdBr 2 ·4H 2 O] and anhydrous [ZnCl 2 ] with N,N'-bidentate N-(pyridin-2-ylmethylene)-cyclopentanamine (impy) in ethanol yields dimeric [(impy)Cd(µ-Br)Br] 2 and monomeric [(impy)ZnCl 2 ] complexes, respectively. The X-ray crystal structure of Cd(II) and Zn(II) complexes revealed that the cadmium atom in [(impy)Cd(µ-Br)Br] 2 and zinc in [(impy)ZnCl 2 ] formed a distorted trigonal-bipyramidal and tetrahedral geometry, respectively. Both complexes showed moderate catalytic activity for the polymerisation of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO), with polymethylmethacrylate (PMMA) syndiotacticity of about 0.70.

show abstract

“…Using the older method of pre-generating the pyridyl imine ligand, a variety of functional groups can be introduced on the phenyl ring, including alkyl groups [21, 23, 24], hydroxides [25], halides [26, 27], additional phenyls [23, 28], and crown ethers [29, 30]. Miguel used compound 2 to not only generate the phenyl species, but also analogs with carboxylic acids and alkynes substituted on the phenyl ring [19, 31]. …”

Section: Introductionmentioning

confidence: 99%

The synthesis of biologically relevant conjugates of Re(CO)3 using pyridine-2-carboxyaldehyde

Costa

Chanawanno

Engle

et al. 2013

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

The new pyridine-2-carboxaldehyde adduct, Re(CO)3(NC6H5C(O)H)Cl 1, and previously reported complex Re(CO)3(NC6H5C(O)H)Br 2 react with aniline derivatives sulfanilamide or 4-aminofluorescein in methanol giving Schiff base conjugates Re(CO)3(pyca-R)X (pyca = pyridinecarbaldehyde imine, X = Cl, Br), 3–6. Pre-isolation of compounds 1 and 2 provides a convenient method for preparing conjugate complexes in addition to the known methods of ligand synthesis and one-pot reactions. All new compounds were completely characterized, and compound 1 and the sulfanilamide derivatives 3 and 4 were structurally elucidated by X-ray crystallography.

show abstract

Carbonyl complexes of manganese, rhenium and molybdenum with 2-pyridylimino acid ligands

Cited by 40 publications

References 45 publications

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO₂ Reduction

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO₂ Reduction

Cd(II) and Zn(II) Complexes Containing N,N'-Bidentate N-(Pyridin-2-ylmethylene)cyclopentanamine: Synthesis, Characterisation and Methyl Methacrylate Polymerisation

The synthesis of biologically relevant conjugates of Re(CO)3 using pyridine-2-carboxyaldehyde

Contact Info

Product

Resources

About

Carbonyl complexes of manganese, rhenium and molybdenum with 2-pyridylimino acid ligands

Cited by 40 publications

References 45 publications

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO2 Reduction

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO2 Reduction

Cd(II) and Zn(II) Complexes Containing N,N'-Bidentate N-(Pyridin-2-ylmethylene)cyclopentanamine: Synthesis, Characterisation and Methyl Methacrylate Polymerisation

The synthesis of biologically relevant conjugates of Re(CO)3 using pyridine-2-carboxyaldehyde

Contact Info

Product

Resources

About

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO₂ Reduction

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO₂ Reduction