Activation of methane by the reactive intermediate tris(trimethylphosphine)osmium(0)

Harper, T. Gregory P.; Shinomoto, Ronald S.; Deming, Mark A.; Flood, Thomas C.

doi:10.1021/ja00231a074

Cited by 52 publications

(14 citation statements)

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“…Offering some hope to counter the discouraging considerations noted above, in the early 1980s, a number of examples were found of transition-metal-based fragments that underwent regioselective oxidative addition of the terminal C–H bonds of n -alkanes. − About the same time, the initial examples of alkane dehydrogenation using well-defined homogeneous transition-metal complexes were reported; − these seemed all the more intriguing in the context of the regioselectivity observed in the “simple” oxidative addition systems.…”

Section: Introductionmentioning

confidence: 99%

Dehydrogenation of Alkanes and Aliphatic Groups by Pincer-Ligated Metal Complexes

2017

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The alkyl group is the most common component of organic molecules and the most difficult to selectively functionalize. The development of catalysts for dehydrogenation of alkyl groups to give the corresponding olefins could open almost unlimited avenues to functionalization. Homogeneous systems, or more generally systems based on molecular (including solid-supported) catalysts, probably offer the greatest potential for regio- and chemoselective dehydrogenation of alkyl groups and alkanes. The greatest progress to date in this area has been achieved with pincer-ligated transition-metal-based catalysts; this and related chemistry are the subject of this review. Chemists are still far from achieving the most obvious and perhaps most attractive goal in this area, the dehydrogenation of simple alkanes to yield alkenes (specifically monoenes) with high yield and selectivity. Greater progress has been made with tandem catalysis and related approaches in which the initial dehydrogenated product undergoes a desirable secondary reaction. Also reviewed is the substantial progress that has been made in the closely related area of dehydrogenation of alkyl groups of substrates containing heteroatoms.

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Section: Introductionmentioning

confidence: 99%

Dehydrogenation of Alkanes and Aliphatic Groups by Pincer-Ligated Metal Complexes

2017

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“…Thus, the first reported examples of alkane dehydrogenation by well-defined soluble transition metal complexes were met with great interest [1][2][3][4][5][6]. Soon thereafter reports of remarkable selectivity in the stoichiometric oxidative addition of C-H bonds appeared, serving to highlight the potential offered by molecular dehydrogenation catalysts [7][8][9][10][11][12][13][14][15] (for some reviews of alkane C-H bond activation by organometallic complexes, see [16][17][18][19][20][21]). …”

Section: Introduction To Alkane Dehydrogenationmentioning

confidence: 99%

Recent Advances in Alkane Dehydrogenation Catalyzed by Pincer Complexes

Kumar

Goldman

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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Olefins are ubiquitous intermediates in the production of fuels and commodity chemicals. Accordingly, the development of methods for the selective dehydrogenation of alkanes to give olefins is a goal with great potential value. Molecular (homogeneous) catalysts appear quite promising in this respect. Great advances have been seen with pincer-ligated catalysts since the mid-1990s, particularly (but not exclusively) with iridium complexes. In this chapter we give an overview of this productive area of research, with emphasis on recent progress.

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“…56 Another group VIII complex, (PMe 3 ) 4 Os(CH 2 t Bu)(H), eliminates neopentane at elevated temperatures and pressures, to generate Os(PMe 3 ) 4 , which adds methane, but again in poor yields (16%; Scheme 4, bottom). 57 Taking advantage of oxidative addition of terminal C-H groups, Chen and Hartwig developed Re(I) photocatalysts for the borylation of alkanes, in some cases regioselectively for the terminal (1 ) C-H position. 58 This type of catalysis was then expanded to Rh systems, and improved when B(II) reagents where utilized.…”

Section: Oxidative Additionmentioning

confidence: 99%