The role of alkane coordination in C–H bond cleavage at a Pt(II) center

Chen, George S.; Labinger, Jay A.; Bercaw, John E.

doi:10.1073/pnas.0610981104

Cited by 67 publications

(49 citation statements)

References 28 publications

(42 reference statements)

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“…X-ray crystallography of S6a ·BAr F and S6c ·BAr F verified the solvent coordination [64]. Diimine analogues, valuable in C–H bond-activation processes, have been extensively reported elsewhere ( S7 ) [65–72]. Later, Tilset’s group prepared and characterized a set of solvento tolyl complexes of the type [Pt(Tol)(N–N)(CH 3 CN)] S8 by means of 1 H and 19 F NMR [73].…”

Section: Reviewmentioning

confidence: 95%

“…Although some of these compounds have been prepared by halogen [58] or methide [74] abstraction as described above, the vast majority of the Pt(II) derivatives stabilized by solvent molecules have been obtained by protonation of neutral alkyl, aryl or hydride Pt(II), as shown in Scheme 8 (see for example: [55,59–60 63,67,69,72,77–81]), or Pt(IV) complexes [96–98]. Nonetheless, this method has not yet been exploited for the preparation of true 14-electron species or agostic stabilized derivatives.…”

Section: Reviewmentioning

confidence: 99%

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True and masked three-coordinate T-shaped platinum(II) intermediates

Ortuño¹,

Conejero²,

Lledós³

2013

Beilstein J. Org. Chem.

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SummaryAlthough four-coordinate square-planar geometries, with a formally 16-electron counting, are absolutely dominant in isolated Pt(II) complexes, three-coordinate, 14-electron Pt(II) complexes are believed to be key intermediates in a number of platinum-mediated organometallic transformations. Although very few authenticated three-coordinate Pt(II) complexes have been characterized, a much larger number of complexes can be described as operationally three-coordinate in a kinetic sense. In these compounds, which we have called masked T-shaped complexes, the fourth position is occupied by a very weak ligand (agostic bond, solvent molecule or counteranion), which can be easily displaced. This review summarizes the structural features of the true and masked T-shaped Pt(II) complexes reported so far and describes synthetic strategies employed for their formation. Moreover, recent experimental and theoretical reports are analyzed, which suggest the involvement of such intermediates in reaction mechanisms, particularly C–H bond-activation processes.

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Section: Reviewmentioning

confidence: 95%

Section: Reviewmentioning

confidence: 99%

True and masked three-coordinate T-shaped platinum(II) intermediates

Ortuño¹,

Conejero²,

Lledós³

2013

Beilstein J. Org. Chem.

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“…Promising alkane-oxidizing inorganic compounds have been discovered, especially Pt complexes following the breakthrough Shilov catalytic system ( Fig. 1) (3)(4)(5)15). Many prominent experimental and computational researchers have made great strides on C-H bond breaking at metal centers, providing mechanistic insights and the identification of discrete compounds or materials for homo-or heterogeneous catalysis.…”

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confidence: 99%

“…Methane constitutes the bulk of abundant natural gas, but its industrial processing requires an energy-and infrastructure-intensive multistep reforming via ''synthesis gas'' (CO plus H 2 ). C-H bond activation has long been a prime obsession of organometallic chemists, for example, and current efforts focus on finding highly active, robust catalysts for mild oxidation of methane and other alkanes (2)(3)(4)15). Promising alkane-oxidizing inorganic compounds have been discovered, especially Pt complexes following the breakthrough Shilov catalytic system ( Fig.…”

mentioning

confidence: 99%

“…None of these systems has yet demonstrated catalytic utility for the industrial scale; all suffer from some combination of low selectivity, catalyst instability, and high temperature and pressure requirements (3,4,15). The holy grail of methane-oxidizing catalyst would be robust toward decomposition, rapid, selective for oxidizing methane to methanol, and active at low temperature and pressure.…”

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confidence: 99%

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A new copper-oxo player in methane oxidation

Himes

Karlin

2009

Proc. Natl. Acad. Sci. U.S.A.

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Methane–to–Methanol Conversion

Hashiguchi

Hövelmann

Bischof

et al. 2005

Encyclopedia of Inorganic Chemistry

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Natural gas (NG) is an abundant, clean, underutilized fossil fuel that can augment or replace petroleum as the feedstock to fuels and chemicals. However, given the relatively high transportation costs for this highly volatile gas, utilization of NG will only be possible if inexpensive, efficient, large‐scale technologies can be developed to chemically convert NG to liquids feedstocks (e.g., long chain alkanes or methanol). Current syngas‐based technologies can carry out this chemical conversion with very high carbon yield (∼70%) while utilizing the only economically viable co‐reactant on this enormous scale: dioxygen or ideally air. However, despite these attractive characteristics, these processes are too expensive to displace petroleum primarily due to the high capital costs associated with the high temperatures required to generate syngas. Substantial effort toward the development of less expensive, lower temperature (<250 °C) processes for the selective, high‐yield oxidative conversion of methane, the major component of NG, to functionalized products has yielded a number of potential systems. This article is focused on one very promising approach: the use of homogenous organometallic and/or inorganic complexes in liquid solutions to mediate the oxidative conversion of methane. Heterogeneous (gas/solid) systems are not covered. Considering the ultimate goal of replacing petroleum with NG, we have organized this article with respect to both fundamental chemistry as well as the important practical considerations of whether or not systems can utilize dixoygen as the ultimate co‐reactant. Two fundamentally different mechanistic strategies have emerged: (i) the use of coordination catalysts that coordinate and cleave the CH bond of methane (defined as CH activation) or that coordinate and activate the co‐reactant (defined as oxidant activation), and (ii) the use of chain reactions based on reactive species such as free radicals or other chain carrying species. Systems that fall into these two categories are further categorized with respect to whether or not oxygen is or can be utilized as the ultimate co‐reactant. The goal is to provide the reader with an efficient way of quickly finding or classifying the rapidly growing body of literature by reaction mechanism and co‐reactant utilized.

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The role of alkane coordination in C–H bond cleavage at a Pt(II) center

Abstract: alkane functionalization ͉ COH activation ͉ catalysis ͉ organometallic chemistry

Cited by 67 publications

References 28 publications

True and masked three-coordinate T-shaped platinum(II) intermediates

True and masked three-coordinate T-shaped platinum(II) intermediates

A new copper-oxo player in methane oxidation

Methane–to–Methanol Conversion

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