Rocha Lima, coord. Getúlio, uma história oral

Costa, Sérgio Amad

doi:10.1590/s0034-75901987000100013

Cited by 2 publications

(2 citation statements)

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“…CVs of complex 5 revealed a reduction with a similar onset potential of −2.1 V (Figure 3a, red trace) to what was observed in the ECE process of CVs with 2° alkyl chlorides (Figure 3a, blue trace). These results are consistent with an S N 2‐like mechanism for activation of both 1° and 2° alkyl chlorides to form Co III (alkyl) intermediates upon electrochemical reduction [49,71] …”

Section: Resultssupporting

confidence: 80%

Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Al Zubaydi,

Onuigbo,

Truesdell

et al. 2023

Angewandte Chemie

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Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt‐catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co‐catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl‐alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C‐Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.

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Section: Resultssupporting

confidence: 80%

Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Al Zubaydi,

Onuigbo,

Truesdell

et al. 2023

Angewandte Chemie

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“…[1,2] Many octahedral organometallic complexes of Co III , such as cobaloxime [2Ϫ10] and Costa's complex [11] (a mixed Schiff base/oxime complex with a uni-negative N 4 equatorial ligand), those with a Schiff base, [12,13] N,NЈ-ethylenebis(actylacetoneiminato), [14] N,NЈ-ethylenebis(salicylideneiminato) [15] and the dianion of disalicylidene-O-phenylenediamine [15] as ligands, have been suggested as models for the vitamin B 12 coenzyme, to mimic either the nature of the active site or a specific function of the enzyme. These model complexes have shown that the ligand in the trans position to the CoϪC bond can affect the kinetics and thermodynamic stability of this bond.…”

Section: Introductionmentioning

confidence: 99%

Equilibrium, Kinetic and Leaving Group Effect Studies on Ligand Substitution Reactions of a Simple Model for Coenzyme B12

Alzoubi

Hamza

Dücker-Benfer

et al. 2002

Eur. J. Inorg. Chem.

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The ligand substitution reactions of trans-[Co III (en) 2 (Me)H 2 O] 2+ and trans-[Co III (en) 2 (Me)NH 3 ] 2+ were studied for CN − , SCN − , N 3 − , and NH 3 as entering nucleophiles. These nucleophiles displace the coordinated H 2 O and NH 3 molecules trans to the methyl group and form the sixcoordinate complex trans-[Co(en) 2 (Me)L]. The complexformation constant for the displacement of H 2 O by NH 3 was found to be 17.4 ± 1.1 M −1 at 20°C, and those for the displacement of NH 3 by SCN − and N 3 − were found to be 4.4 ± 1.5 and 3.1 ± 0.4 at 10°C, respectively. From temperature and pressure dependence studies, activation parameters (∆H ϶ , ∆S ϶ and ∆V ϶ ) for the reaction of trans-[Co III (en) 2 (Me)H 2 O] 2+

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Rocha Lima, coord. Getúlio, uma história oral

Abstract: de quantidade de estudos já publicados do que de formular reais propostas de avanco teórico-metodológico no campo da administração. A de-

Cited by 2 publications

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Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Equilibrium, Kinetic and Leaving Group Effect Studies on Ligand Substitution Reactions of a Simple Model for Coenzyme B12

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