Photooxidation of the molybdenum and tungsten carbynes (.eta.5-C5H5)L2M.tplbond.CR [L = P(OMe)3, CO and R = Ph, Me, c-C3H5]

Carter, John D.; Kingsbury, Kevin B.; Wilde, Andreas; Schoch, Thomas K.; Leep, Carolyn J.; Pham, Eric K.; McElwee‐White, Lisa

doi:10.1021/ja00008a025

Cited by 47 publications

(45 citation statements)

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“…As part of our efforts to understand the photooxidation of complexes Va-Vf, we carried out a UV-visible spectroscopic study of the various compounds (29). Figure 1 shows the UV-visible spectrum of (η 5 -C 5 H 5 )[P(OMe) 3 ] 2 Mo=CPh (Va).…”

Section: Electronic Structure and Spectroscopy Of Metal Carbynesmentioning

confidence: 99%

“…For example, (rç-C 5 H 5 )[P(OMe) 3 ](CO)W=CPh (Vd) has a lifetime of 140 ns in solution at room temperature (29). Bocarsly et al (31) reported that luminescence of the emissive complexes X(CO) 2 L 2 W=CPh was quenched by a variety of organic compounds at rates dependent on the triplet energy of the quencher.…”

Section: Electronic Structure and Spectroscopy Of Metal Carbynesmentioning

confidence: 99%

“…Extended Hiickel calculations on metal carbynes of the type (η 5 -C 5 H 5 )L 1 L 2 Mo=CR (29,34) suggest that the highest occupied molecular orbital (HOMO) of the complexes should be primarily metal d in charac ter, and that the lowest unoccupied molecular orbital (LUMO) is com posed of one of the metal-carbon π* orbitals. Figure 2 shows a partial molecular orbital diagram for the formation of the model compound (η 5 -C 5 H 5 )[P(OH) 3 ] 2 Mo=CPh from the fragments (Î?…”

Section: Electronic Structure and Spectroscopy Of Metal Carbynesmentioning

confidence: 99%

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Photooxidation of Metal Carbynes

McElwee‐White

Kingsbury

Carter

1993

Photosensitive Metal—Organic Systems

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Radical cations formed upon photooxidation of the metal carbyne complexes (n 5 -C 5 H 5 )L 1 L 2 M≡CR (M is Mo or W; L 1 and L 2 are CO or P(OMe) 3 ; and R is alkyl or aryl) were found to be extremely reactive. Depending on the reaction conditions, either the radical cations exhibited the ligand-exchange and atom--abstraction processes that are typical of metal radicals, or the carbyne ligands underwent a series of highly unusual rearrangements to yield organic products. When organic products were generated, they were formed with good stereochemical and regiochemical control.REACTIVE ORGANIC FRAGMENTS CAN BE STABILIZED with transi tion metals so that they can be used for synthesis under ordinary reaction conditions. One example is the extensive utilization of metal carbenes in organic synthesis (2). It is thus somewhat surprising that there are so few reported cases of generation of organic products from the closely related metal carbynes. Although the chemistry of metal carbynes has been explored (2), most of the reported reactions involve conversion into other carbyne complexes by exchange of ancillary ligands; interconversion of car byne, carbene, and vinylidene complexes; or [2 + 2] cycloaddition with alkenes and alkynes followed by metathesis or polymerization. With the exception of polymers and metathesis products, organic species derived from the carbyne ligand are almost never generated.One method for inducing new modes of reactivity in metal complexes is one-electron (l-e~) oxidation. The differences in reaction rates between 18-e~ complexes and their 17-e~ counterparts can be quite dramatic (3-5). Reaction manifolds that are not available to an 18-e~ complex can thus become accessible to its corresponding 17-e~ radical cation. This chapter

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Section: Electronic Structure and Spectroscopy Of Metal Carbynesmentioning

confidence: 99%

Section: Electronic Structure and Spectroscopy Of Metal Carbynesmentioning

confidence: 99%

Section: Electronic Structure and Spectroscopy Of Metal Carbynesmentioning

confidence: 99%

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Photooxidation of Metal Carbynes

McElwee‐White

Kingsbury

Carter

1993

Photosensitive Metal—Organic Systems

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“…Transition metal-alkylidynes, also known as metal-carbyne complexes [1][2][3][4] have been extensively studied over nearly four decades since their discovery. 5 Much of the interest in these compounds has been focused upon their diverse and fascinating reactivity, specially the catalytic metathesis of alkynes; [6][7][8][9][10][11][12][13][14] although many other aspects of their chemistry have also been explored, including the luminescence properties of their electronic states where the excited-state electron-transfer reactions of transition metal chromophores are integral to homogeneous systems for articial photosynthesis, dye-sensitized solar cells, and photoredox-based methods for organic synthesis, among other applications [15][16][17][18][19][20][21][22][23][24][25][26][27] and their utility as building blocks for electronic materials. [28][29][30][31][32][33][34][35][36] Regarding photophysical studies of the metal carbyne complexes of the half-sandwich type Cp(CO){P(OMe) 3 }M^C-R, where M ¼ Mo, W and R ¼ aryl, a reported was made by McElwee-White.…”

Section: Introductionmentioning

confidence: 99%

“…[28][29][30][31][32][33][34][35][36] Regarding photophysical studies of the metal carbyne complexes of the half-sandwich type Cp(CO){P(OMe) 3 }M^C-R, where M ¼ Mo, W and R ¼ aryl, a reported was made by McElwee-White. 37,38 These complexes display weak absorption bands in the visible region and long-lived luminescence. Theoretical and spectroscopic studies indicate that the low energy band is associated with the HOMO / LUMO transition, which is dominated by the d(M) / p*(M^C-Ar) conguration.…”

Section: Introductionmentioning

confidence: 99%

Photophysics of tungsten–benzylidyne complexes derived from s-indacene: synthesis, characterization and DFT studies

et al. 2015

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Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Bitterwolf¹

2005

Encyclopedia of Inorganic Chemistry

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Photochemistry has evolved into a powerful tool for the highly selective generation of reactive intermediates in inorganic and organometallic chemistry. This review examines the state of the art in the examination of mechanisms of photochemical reactions utilizing techniques such as frozen matrices and fast time‐resolved methods. The application of photochemistry to the preparation of dihydrogen, alkane, and noble gas intermediates is reviewed along with the significance of these intermediates in the understanding of the mechanism of oxidative addition processes. Experiment and theory of charge transfer phenomena are extensively discussed along with the application of these processes to semiconductor and biochemical studies. Applications of photocrystallography to the examination of linkage isomers and very short‐lived excited state species are reviewed. Finally, a number of examples of the application of photochemical reactions, such as the photolysis of Fisher carbene species to generate ketenelike intermediates, to synthesis are discussed. The literature is reviewed to the end of 2003.

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Photooxidation of the molybdenum and tungsten carbynes (.eta.5-C5H5)L2M.tplbond.CR [L = P(OMe)3, CO and R = Ph, Me, c-C3H5]

Cited by 47 publications

References 3 publications

Photooxidation of Metal Carbynes

Photooxidation of Metal Carbynes

Photophysics of tungsten–benzylidyne complexes derived from s-indacene: synthesis, characterization and DFT studies

Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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