[MnBrL(CO)<sub>4</sub>] (L = Amidinatogermylene): Reductive Dimerization, Carbonyl Substitution, and Hydrolysis Reactions

Cabeza, Javier A.; García‐Álvarez, Pablo; Gobetto, Roberto; González‐Álvarez, Laura; Nervi, Carlo; Pérez‐Carreño, Enrique; Polo, Diego

doi:10.1021/acs.organomet.6b00168

Cited by 34 publications

(11 citation statements)

References 111 publications

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“…Some amidinatogermylenes–– and ‐silylenes react with transition metals to give products that result from the insertion of the metal atom into an E−N bond of the corresponding amidinatotetrylene reagent. However, the ring expansion of an amidinatotetrylene by insertion of an organic fragment has only been reported as the result of two very specific reactions that do not involve carbene reagents: a thiocarbonyl group (that arises from CS 2 ) has been inserted into a Si−N bond of a bis(guanidinato)silylene and a 4‐MeOC 6 H 4 CMe fragment (that arises from the ketone 4‐MeOC 6 H 4 C(O)Me) has been inserted into a Ge−N bond of an amidinatogermylene‐borane Lewis pair …”

Section: Methodsmentioning

confidence: 99%

First Insertions of Carbene Ligands into Ge−N and Si−N Bonds

Álvarez-Rodríguez

Cabeza

García‐Álvarez

et al. 2017

Chemistry A European J

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The insertion of carbene ligands into Ge-N (three examples) and Si-N (one example) bonds has been achieved for the first time by treating Fischer carbene complexes (M=W, Cr) with bulky amidinatotetrylenes (E=Ge, Si). These reactions, which start with a nucleophilic attack of the amidinatotetrylene heavier group 14 atom to the carbene C atom, proceed through a stereoselective insertion of the carbene fragment into an E-N bond of the amidinatotetrylene ENCN four-membered ring, leading to [M(CO) L] derivatives in which L belongs to a novel family of tetrylene ligands comprising an ECNCN five-membered ring.

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Section: Methodsmentioning

confidence: 99%

First Insertions of Carbene Ligands into Ge−N and Si−N Bonds

Álvarez-Rodríguez

Cabeza

García‐Álvarez

et al. 2017

Chemistry A European J

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“…Two mechanisms have been proposed 10,[14][15][16][17][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 the dimer [Mn(CO) 3 ( -diimine)] 2 at a more negative potential than the parent complex generating the five-coordinate anion [Mn(CO) 3 ( -diimine)] to which CO 2 coordinates and is catalyti-cally reduced in the presence of a Brönsted acid (the source of H + ).…”

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confidence: 99%

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

et al. 2016

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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 ...

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“…Transition metal (M) complexes containing HT ligands have been known for more than 40 years, however, the investigation of their applicability in the field of homogeneous catalysis is as yet in its initial stages,[2a], particularly in comparison with that of NHC complexes . Such a dissimilar situation is mainly a consequence of the generally lower stability of HT‐M complexes, since degradation reactions involving oxidation, hydrolysis and substitution processes are well known for systems of this kind. However, the last few years have witnessed the appearance of a family of bi‐ and tridentate ligands containing one or more HTs as donor groups that not only present significant catalytic activities in a number of organic transformations but have also shown that the HT groups play a steering role in the catalytic reactions.…”

Section: Introductionmentioning

confidence: 99%

“…In 2016, stimulated by the above‐commented very interesting features of both HTs and pincer ligands, by the absence of metal‐free pincer ligands having an HT as the central donor group of the pincer framework, and taking advantage of our experience working with HTs,[2f], [2g], , , , [9b], [22a], [22b], our research group embarked the pincer‐type HT ship by preparing the first germylene and stannylene flanked by two phosphane groups. Phosphanes were chosen as side donor groups because, in addition to having excellent properties as ligands (they can be bulky and strong electron donors), they facilitate the monitoring of their reactions (by 31 P NMR).…”

Section: Introductionmentioning

confidence: 99%

The Transition Metal Chemistry of PGeP and PSnP Pincer Heavier Tetrylenes

2020

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This review article collects and discusses the syntheses of the currently known metal‐free heavier tetrylenes having a PEP pincer topology (E = tetrel atom) as well as their transition metal derivative chemistry. To date, only five PGeP germylenes and two PSnP stannylenes have been isolated. These compounds have been successfully synthesized by treating GeCl2(diox) (diox = 1,4‐dioxane), GeCl2(NHC) (NHC = N‐heterocyclic carbene) or SnCl2 with two equivalents of an appropriate lithiated phosphine. Their transition metal chemistry is dominated by processes in which, in addition to the coordination of one or both phosphane groups, the E atom ends inserted into M–M or M–X (X = anionic group) bonds. Only in a few occasions a simple coordination of the tetrylene fragment (as a neutral two‐electron‐donor ligand) has been observed. The structural and bonding characteristics of the metal‐free PEP tetrylenes and of relevant examples of their transition metal derivatives are also surveyed.

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[MnBrL(CO)₄] (L = Amidinatogermylene): Reductive Dimerization, Carbonyl Substitution, and Hydrolysis Reactions

Cited by 34 publications

References 111 publications

First Insertions of Carbene Ligands into Ge−N and Si−N Bonds

First Insertions of Carbene Ligands into Ge−N and Si−N Bonds

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

The Transition Metal Chemistry of PGeP and PSnP Pincer Heavier Tetrylenes

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[MnBrL(CO)4] (L = Amidinatogermylene): Reductive Dimerization, Carbonyl Substitution, and Hydrolysis Reactions

Cited by 34 publications

References 111 publications

First Insertions of Carbene Ligands into Ge−N and Si−N Bonds

First Insertions of Carbene Ligands into Ge−N and Si−N Bonds

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

The Transition Metal Chemistry of PGeP and PSnP Pincer Heavier Tetrylenes

Contact Info

Product

Resources

About

[MnBrL(CO)₄] (L = Amidinatogermylene): Reductive Dimerization, Carbonyl Substitution, and Hydrolysis Reactions

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