Rearrangement of a propargyl vinyl rhenium complex to a rhenium allenyl vinyl ketone complex

Casey, Charles P.; Underiner, Todd L.; Vosejpka, Paul C.; Gavney, James A.; Kiprof, Paul

doi:10.1021/ja00053a019

Cited by 13 publications

(8 citation statements)

References 6 publications

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“…These two strategies differ in how new drugs are identified. One uses the three-dimensional structure of a target protein in combination with computer modeling to identify potential drug candidates (9). The other, which does not require knowledge of tertiary structure, is based upon the vast information content of amino acid or nucleotide (nt) sequences.…”

Section: Discussionmentioning

confidence: 99%

“…The temperature regime of the hydrothermal method is lower than that of the flux method. and in fact interesting exam-ples of hydrothermal crystallization at room temperature and even at ice temperature have recently been found (9). More typically these reactions are carried out in closed vessels above the normal boilingpoint of the solvent, at temperatures up to about 400°C.…”

Section: Flux and Hydrothermal Syntheses-hot But Not Too Hotmentioning

confidence: 99%

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Turning Down the Heat: Design and Mechanism in Solid-State Synthesis

Stein

Keller

Mallouk

1993

Science

556

296

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Solid-state compounds have historically been prepared through high-temperature solid-solid reactions. New mechanistic understanding of these reactions suggests possible routes to metastable compositions and structures as well as to thermodynamically stable, low-temperature phases that decompose at higher temperatures. Intermediate-temperature synthetic techniques, including flux and hydrothermal methods, as well as low-temperature intercalation and coordination reactions, have recently been developed and have been used to prepare unprecedented materials with interesting electronic, optical, and catalytic properties. The trend in modern solid-state synthesis resembles increasingly the approach used in small-molecule chemistry, in the sense that attention to reaction mechanism and the use of molecular building blocks result in an ability to prepare new materials of designed structure.

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Section: Discussionmentioning

confidence: 99%

Section: Flux and Hydrothermal Syntheses-hot But Not Too Hotmentioning

confidence: 99%

Turning Down the Heat: Design and Mechanism in Solid-State Synthesis

Stein

Keller

Mallouk

1993

Science

556

296

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“…6 Rhenium can also form classical and nonclassical hydride complexes, including octahedral ReH 6 3-, which are significant in organometallic chemistry and catalytic process. [7][8][9] The intensities of Re-H stretching vibrations in rhenium hydride complexes are extremely weak and are not observed spectroscopically. Finally, reactions of naked rhenium with molecular hydrogen have not yet been investigated experimentally although theoretical calculations have suggested that the Re( 6 S) ground state does not insert into H 2 spontaneously.…”

Section: Introductionmentioning

confidence: 99%

Matrix Infrared Spectra and Density Functional Theory Calculations of Manganese and Rhenium Hydrides

Wang

Andrews

2003

J. Phys. Chem. A

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Laser-ablated Mn and Re atoms react with H 2 upon co-condensation in excess argon and neon and in pure hydrogen to produce metal hydrides. The reaction products are identified through isotopic substitution (D 2 , HD, and H 2 + D 2 ) and density functional theory calculations. The 7 Σ + ground state diatomic MnH is observed at 1493.3 cm -1 in solid neon, 1486.4 cm -1 in hydrogen, and 1477.9 cm -1 in argon. The ReH molecule gives a sharp band at 1985.0 cm -1 in argon, which is suggested to be the 5 Σ + ground state by DFT calculations. The MnH 2 molecule provides ν 3 modes at 1600.8 cm -1 in solid neon, 1598.0 cm -1 in solid hydrogen, and 1592.3 cm -1 in solid argon, and the analogous ReH 2 molecule absorbs at 1646.4 cm -1 in solid argon. In addition MnH 2is observed at 1465.6 cm -1 in solid neon. The bonding properties of the first row transition metal dihydrides are compared, and reaction mechanisms of Mn and Re with H 2 are discussed. The novel ReH 4 molecule absorbs at 2037.2 and 590.6 cm -1 . This work reports the first experimental evidence for neutral rhenium hydride molecules.

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“…Exclusion of Hydrogen Transfer between Vinyl and Allyl Groups. In related studies of the rearrangement of a propargyl vinyl rhenium complex to an allenyl vinyl ketone complex, we discovered that the rhenium allenyl vinyl ketone complex Cp(CO)Re(η 2 ,η 2 -CH 2 CCHCOCHCHCH 2 CMe 3 ) ( 16 ) stereospecifically transferred a hydrogen from the β-vinyl position of the enone ligand to the central carbon of the η 2 -allene ligand to produce an η 3 -allyl vinyl ketone complex Cp(CO)Re(η 3 -CH 2 CHCHCOCHCCH 2 CMe 3 ) ( 17 ) …”

Section: Resultsmentioning

confidence: 99%

Rearrangement of Rhenium Allyl Vinyl Ketone Complexes

et al. 1997

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The isomerization of parallel−perpendicular allyl vinyl ketone complex C5H5(CO)Re(η2,η2-H2CCHCH2COCHCHCH2CMe3) (2) to the diastereomeric perpendicular−parallel complex C5H5(CO)Re(η2,η2-H2CCHCH2COCHCHCH2CMe3) (6) occurred without formation of an unsaturated intermediate trappable by either PMe3 or 13CO. The rearrangement of exo -C5H5(CO)Re[η2,η2-CH2CHCH(CH3)COCHCHCH2CMe3] (8-exo) occurred with retention of stereochemistry at rhenium and with enantioface inversion of both complexed alkenes. The kinetically formed parallel−perpendicular isomer 8-exo rearranged by sequential enantioface inversion of the vinyl π-bond to give parallel−parallel intermediate exo -C5H5(CO)Re[η2,η2-CH2CHCH(CH3)COCHCHCH2CMe3] (12-exo) and then enantioface inversion of the allyl π-bond to form the perpendicular−parallel isomer exo -C5H5(CO)Re[η2,η2-CH2CHCH(CH3)COCHCHCH2CMe3] (9-exo). Enolization of allyl vinyl ketone complexes was observed, but is not required for the isomerization. C−H insertion mechanisms involving a net hydrogen migration were excluded by deuterium labeling studies. A mechanism in which rhenium migrates to the opposite enantiofaces of the alkene ligands via σ-C−H complexes is proposed.

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Rearrangement of a propargyl vinyl rhenium complex to a rhenium allenyl vinyl ketone complex

Cited by 13 publications

References 6 publications

Turning Down the Heat: Design and Mechanism in Solid-State Synthesis

Turning Down the Heat: Design and Mechanism in Solid-State Synthesis

Matrix Infrared Spectra and Density Functional Theory Calculations of Manganese and Rhenium Hydrides

Rearrangement of Rhenium Allyl Vinyl Ketone Complexes

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