Two-electron photoelimination reactions from edge-sharing bioctahedral dimolybdenum(III) complexes

Pistorio, Bradford J.; Nocera, Daniel G.

doi:10.1039/a904143e

Cited by 13 publications

(26 citation statements)

References 17 publications

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“…1 H NMR spectra (500 MHz) were referenced to TMS using the residual proteo impurities of the given solvent. 31 P{ 1 H} NMR spectra (202.5 MHz) were referenced to an external 85% H3PO4 standard. All chemical shifts are reported using the standard δ notation in parts-per-million; positive chemical shifts are to a higher frequency from the given reference.…”

Section: Methodsmentioning

confidence: 99%

“…[22][23][24][25] As anticipated for the reactivity of two-electron mixed-valence cores, this MMCT excited state promotes two-electron photoredox transformations involving quadruply bonded metal-metal complexes. [26][27][28][29][30][31] When a photon cannot be used to drive the formation of a two-electron mixedvalence intermediate, a ground-state M n+2 ‚‚‚M n species must be stabilized relative to its symmetric M n+1 ‚‚‚M n+1 congener. Yet the paucity of molecular compounds displaying two-electron mixed-valence cores highlights the inability of common ligand systems to preferentially promote this internal disproportionation.…”

Section: Introductionmentioning

confidence: 99%

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Hydrido, Halo, and Hydrido-Halo Complexes of Two-Electron Mixed-Valence Diiridium Cores

and

Nocera

2000

J. Am. Chem. Soc.

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Two-electron mixed-valence bimetallic cores of iridium are stabilized in a diphosphazane, MeN[P(OCH2CF3)2]2 (bis(bis(trifluoroethoxy)phosphino)methylamine, tfepma) coordination sphere. Treatment of [Ir(cod)Cl]2 with tfepma affords the Ir2 0,II complex, Ir2(tfepma)3Cl2 (1), in which the Ir0 and IrII centers assume trigonal bipyramidal and square pyramidal coordination geometries, respectively. The coordinatively unsaturated two-electron mixed-valence core of 1 supports an extensive acid−base and oxidation−reduction chemistry. As established by single crystal X-ray analysis, two-electron donor ligands are readily received at the IrII center of 1 to complete the octahedral coordination environment that is preferred by a d7 metal−metal bonded center. Alternatively, redox-active substrates rapidly add across the single metal−metal bond of 1 to form Ir2 I,III mixed-valence complexes; the chlorine and hydrochloric acid adducts, Ir2(tfepma)3Cl4 (5) and Ir2(tfepma)3HCl3 (7b), respectively, have been characterized by NMR spectroscopy and X-ray crystallography. Likewise, H2 reacts with 1 to afford an Ir2 I,III dihydride complex, Ir2(tfepma)3H2Cl2 (8). Single-crystal X-ray and NMR analyses of 8 reveal that a single hydride ligand is coordinated at each iridium center of the bimetallic core. Hydrogen is readily removed from the complex in solution and the solid state, providing the first example of the reversible addition of dihydrogen across a single metal−metal bond.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hydrido, Halo, and Hydrido-Halo Complexes of Two-Electron Mixed-Valence Diiridium Cores

and

Nocera

2000

J. Am. Chem. Soc.

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“…The same zwitterionic intermediate supports two-electron elimination reactions of isovalent ESBO complexes (the photodriven reverse of eq (4)). 45 Whereas the two electron zwitterionic intermediate may be trapped by a proton as well (see Figure 5), the ensuing species is not hydridic enough to be protonated to produce hydrogen.…”

Section: A Chemist’s Toolbox For Catalysis Of Consequence To Renewmentioning

confidence: 99%

Chemistry of Personalized Solar Energy

2009

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Personalized energy (PE) is a transformative idea that provides a new modality for the planet’s energy future. By providing solar energy to the individual, an energy supply becomes secure and available to people of both legacy and non-legacy worlds, and minimally contributes to increasing the anthropogenic level of carbon dioxide. Because PE will be possible only if solar energy is available 24 hours a day, 7 day a week, the key enabler for solar PE is an inexpensive storage mechanism. HX (X = halide or OH−) splitting is a fuel-forming reaction of sufficient energy density for large scale solar storage but the reaction relies on chemical transformations that are not understood at the most basic science level. Critical among these are multielectron transfers that are proton-coupled and involve the activation of bonds in energy poor substrates. The chemistry of these three italicized areas is developed, and from this platform, discovery paths leading to new HX and H2O splitting catalysts are delineated. For the case of the water splitting catalyst, it captures many of the functional elements of photosynthesis. In doing so, a highly manufacturable and inexpensive method has been discovered for solar PE storage.

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“…2) [6]. A number of other compounds of the type Ar 2 PCH 2 PAr 2 have also been prepared [7][8][9][10][11][12][13][14]. Recent research in our group has concerned the synthesis of new small bite angle diphosphines based on the dppm framework.…”

Section: Introductionmentioning

confidence: 99%

Small bite angle diphosphines: synthesis of Ph(p-tolyl)PCH2PPh(p-tolyl) upon lithium reduction of Ph2P(p-tolyl)—molecular structure of anti-[Mo(CO)4{Ph(p-tolyl)PCH2PPh(p-tolyl)}]

Hogarth

Kilmartin

2008

Transition Met Chem

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Two-electron photoelimination reactions from edge-sharing bioctahedral dimolybdenum(III) complexes

Cited by 13 publications

References 17 publications

Hydrido, Halo, and Hydrido-Halo Complexes of Two-Electron Mixed-Valence Diiridium Cores

Hydrido, Halo, and Hydrido-Halo Complexes of Two-Electron Mixed-Valence Diiridium Cores

Chemistry of Personalized Solar Energy

Small bite angle diphosphines: synthesis of Ph(p-tolyl)PCH2PPh(p-tolyl) upon lithium reduction of Ph2P(p-tolyl)—molecular structure of anti-[Mo(CO)4{Ph(p-tolyl)PCH2PPh(p-tolyl)}]

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