Insertion by Triplet Methylene Radicals in Alkane System<sup>1</sup>

Ring, D. F.; Rabinovitch, B. S.

doi:10.1021/ja00970a047

Cited by 18 publications

(3 citation statements)

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“…One of the key features of NHCs compared to other classes of carbenes is their stability. Simple carbenes, like the parent methylidene (“CH 2 ”, 1 , Chart ), decompose above cryogenic temperatures, cyclopropanate alkenes, , dimerize, − and insert into otherwise unreactive C–H bonds. ,, These reactions can be violently exothermic . In contrast, NHCs can be stored, bottled, and even distilled. , Although NHCs are far superior in stability to other types of carbenes, they still do not surpass the stability of classic phosphines such as PPh 3 .…”

Section: Introductionmentioning

confidence: 99%

N-Heterocyclic Carbenes in Materials Chemistry

et al. 2019

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N-Heterocyclic carbenes (NHCs) have become one of the most widely studied class of ligands in molecular chemistry and have found applications in fields as varied as catalysis, the stabilization of reactive molecular fragments, and biochemistry. More recently, NHCs have found applications in materials chemistry and have allowed for the functionalization of surfaces, polymers, nanoparticles, and discrete, well-defined clusters. In this review, we provide an in-depth look at recent advances in the use of NHCs for the development of functional materials.

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Section: Introductionmentioning

confidence: 99%

N-Heterocyclic Carbenes in Materials Chemistry

et al. 2019

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“…A comparison in each alkane system of the ratio of the total amount of radicals formed, ( R1)/(. R) (based on reactions [5]- [7], [13], [14], disproportionation being taken into account) revealed reasonable agreement between the ratios from classes C,,,, and C,,,. However, the C,,, class indicated a different (smaller) ( .…”

Section: Insertion Reactionsmentioning

confidence: 92%

“…It has also been suggested that in some systems 'CH, may abstract H from a C-H bond (5). Triplet methylene ( 3 C~, ) is now known to abstract H from C-H bonds (2c, 2d, 6), may insert into these (7), and also adds non-stereospecifically to C==C bonds (la, 4b, 8). The present study was 'This work was supported by the Office of Naval Research.…”

Section: Introductionmentioning

confidence: 99%

Reactions of triplet methylene radicals with alkanes

Ring¹,

Rabinovitch²

1968

Can. J. Chem.

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Studies have been made of the products resulting from reaction between triplet methylene and several alkanes, propane, ti-butane, and isobutane. Triplet methylene was produced by photolysis of diazomethane in the presence of a large excess of inert nitrogen gas. Complicating side reactions involving diazomethane were encountered.Observation of higher products allowed the determination of the relative rates of 1°:2":3" H abstraction from C-H bonds; these are -1:14:150. The rate of addition of 3CHt to the C=C bond in ethylene appears to proceed -3.5 times faster than H abstraction from a 3 C-H bond. The possible occurrence of insertion by into C-H bonds is discussed and relative rates of insertion for 1°:2":3" bonds are deduced to be -1 :2:7. Comparisons of the relative rates of inserti0n:abstraction are also given. Studies with propane-d, indicated an isotope effect for abstraction of H:D from the l o position of -3.9; insertion by 3CHz into the same position showed an isotope effect of --2.

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