Catalytic Degenerate and Nondegenerate Oxygen Atom Transfers Employing N2O and CO2 and a MII/MIV Cycle Mediated by Group 6 MIV Terminal Oxo Complexes

Yonke, Brendan L.; Reeds, Jonathan P.; Zavalij, Peter Y.; Sita, Lawrence R.

doi:10.1002/anie.201106074

Cited by 56 publications

(70 citation statements)

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“…65 Again, rather harsh reactions conditions were applied. 70 They were able to demonstrate the catalytic oxidation of an isocyanide to an isocyanate (Scheme 8). They have shown that the Ru(II) complex Ru(TMP)(THF) 2 can be oxidized with N 2 O to give Ru(TMP)(O)(THF) or Ru(TMP)(O) 2 , depending on the reaction conditions.…”

Section: Metal-catalyzed Reactions With N 2 Omentioning

confidence: 99%

Synthetic chemistry with nitrous oxide

2015

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This review article summarizes efforts to use nitrous oxide (N2O, 'laughing gas') as a reagent in synthetic chemistry. The focus will be on reactions which are carried out in homogeneous solution under (relatively) mild conditions. First, the utilization of N2O as an oxidant is discussed. Due to the low intrinsic reactivity of N2O, selective oxidation reactions of highly reactive compounds are possible. Furthermore, it is shown that transition metal complexes can be used to catalyze oxidation reactions, in some cases with high turnover numbers. In the final part of this overview, the utilization of N2O as a building block for more complex molecules is discussed. It is shown that N2O can be used as an N-atom donor for the synthesis of interesting organic molecules such as triazenes and azo dyes.

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Section: Metal-catalyzed Reactions With N 2 Omentioning

confidence: 99%

Synthetic chemistry with nitrous oxide

2015

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“…Finally, in comparing the differences in imido group reactivity for R = SiMe 3 vs CMe 3 in the case of 4 + 13 CO, variable-temperature NMR revealed that a fast dynamic process observed at room temperature is within the slow exchange limit at −70°C. At this latter temperature, characteristic 13 3 The room-temperature solution stability of 13 provided an opportunity to prepare this compound on a preparative scale, and indeed, it was isolated in a 75% yield as an analytically pure crystalline material, which was further subjected to single-crystal X-ray crystallography. Quite surprisingly, efforts to isolate 14 were also successful through fortuitous crystallization from solution at −30°C of a mixture consisting of a racemate of this C 1 -symmetric complex and the starting imido 4.…”

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confidence: 99%

“…Equally exciting in this respect is that, for the group 6 metals, the CPAM ligand environment also appears capable of modulating the strength of metal−oxygen and metal−nitrogen multiple bonds to the extent required for productive formation of new bonds that includes the productive release of products through atom-and group-transfer processes required for catalytic turnover. 3,4 ■ ASSOCIATED CONTENT…”

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confidence: 99%

Catalytic Production of Isocyanates via Orthogonal Atom and Group Transfers Employing a Shared Formal Group 6 M(II)/M(IV) Redox Cycle

et al. 2014

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Under an atmosphere of CO, the Mo(IV) imido complex Cp*Mo[N(iPr)C(Me)N(iPr)](NSiMe3) (Cp* = η5-C5Me5) (1) serves as a catalyst for production of an isocyanate via metal-mediated nitrene group transfer in benzene solution under mild conditions (55 °C, 10 psi) according to RN3 + CO → N2 + RNCO. Mechanistic and structural studies support a catalytic cycle for nitrene group transfer involving formal Mo(II) monocarbonyl and Mo(IV) (κ2-C,N)-isocyanate intermediates. These results complement an earlier finding that catalytic production of isocyanates can alternatively proceed through oxygen-atom transfer and an isomeric Mo(IV) (κ2-C,O)-isocyanate according to N2O + CNR → N2 + RNCO.

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“…Aresta's initial discovery was a seminal breakthrough in the development of molecular catalysts for artificial carbon dioxide fixation. Indeed, the ligation of CO 2 to metal centers is well studied in regards to molecular structure and stoichiometric reactivity [11,[15][16][17][18]. Complementary to metal-mediated activation of carbon dioxide, there is an increasing interest to develop carboxylations that do not require transition metals.…”

Section: Introductionmentioning

confidence: 99%