Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle

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

doi:10.1021/ja208669s

Cited by 40 publications

(36 citation statements)

References 26 publications

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“…93 The reaction product can be isolated and is stable as a solid if stored at À35 1C. 98,99 The formation of stable covalent adducts of N 2 O can be achieved without transition metals. Apart from an alkylation reaction with MeO 3 SCF 3 (O-and b-N-alkylation), it was shown that the complex can be reduced to give a stable radical anion.…”

Section: N 2 O As N-atom Donormentioning

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: N 2 O As N-atom Donormentioning

confidence: 99%

Synthetic chemistry with nitrous oxide

2015

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“… 9 Sita and co-workers developed a homogeneous version of this transformation, mediated by the Mo( ii ) complex, Cp*Mo(NCN)(CO) 2 (NCN = i PrNC(Me)N i Pr). 10 In this process, N 2 O oxidizes Cp*Mo(NCN)(CO) 2 to form a Mo( iv ) oxo, Cp*Mo(NCN)(O), which then reacts with CO to form CO 2 and regenerate Cp*Mo(NCN)(CO) 2 . However, an N–N bond cleavage reaction, which results in irreversible formation of Cp*Mo(NCN)(NCO)(NO), was found to be competitive with oxo formation.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N₂O reduction

Hartmann

Hayton

2018

Chem. Sci.

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“…8 An additional example has a molybdenum(II) dicarbonyl form an isocyanate concomitant with N 2 O cleavage. 9 In all these examples, however, the nitrogen source is an azide or N 2 O. Two examples of (µ 2 ,η 1 ,η 2 -N 2 )Hf 2 complexes show N 2 cleavage that is facilitated by reduction with CO to form an equivalent of isocyanate for each mole of N 2 (Fig.…”

Section: Introductionmentioning

confidence: 99%

Experimental and computational studies on the formation of cyanate from early metal terminal nitrido ligands and carbon monoxide

et al. 2014

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An important challenge in the artificial fixation of N2 is to find atom efficient transformations that yield value-added products. Here we explore the coordination complex mediated conversion of ubiquitous species, CO and N2, into isocyanate. We have conceptually split the process into three steps: (1) the six-electron splitting of dinitrogen into terminal metal nitrido ligands, (2) the reduction of the complex by two electrons with CO to form an isocyanate linkage, and (3) the one electron reduction of the metal isocyanate complex to regenerate the starting metal complex and release the product. These steps are explored separately in an attempt to understand the limitations of each step and what is required of a coordination complex in order to facilitate a catalytic cycle. The possibility of this cyanate cycle was explored with both Mo and V complexes which have previously been shown to perform select steps in the sequence. Experimental results demonstrate the feasibility of some of the steps and DFT calculations suggest that, although the reduction of the terminal metal nitride complex by carbon monoxide should be thermodynamically favorable, there is a large kinetic barrier associated with the change in spin state which can be avoided in the case of the V complexes by an initial binding of the CO to the metal center followed by rearrangement. This mandates certain minimal design principles for the metal complex: the metal center should be sterically accessible for CO binding and the ligands should not readily succumb to CO insertion reactions.

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Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle

Cited by 40 publications

References 26 publications

Synthetic chemistry with nitrous oxide

Synthetic chemistry with nitrous oxide

Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N₂O reduction

Experimental and computational studies on the formation of cyanate from early metal terminal nitrido ligands and carbon monoxide

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Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle

Cited by 40 publications

References 26 publications

Synthetic chemistry with nitrous oxide

Synthetic chemistry with nitrous oxide

Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N2O reduction

Experimental and computational studies on the formation of cyanate from early metal terminal nitrido ligands and carbon monoxide

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Synthesis and reactivity of a nickel(ii) thioperoxide complex: demonstration of sulfide-mediated N₂O reduction