A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand.

A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand. Research Abstract Details 

Research Abstract Table of Contents

Jump to the:

A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand. Abstract Text:

Oleg V Ozerov,Lori A Watson,Maren Pink,Kenneth G Caulton,

The molecule (PNPR)Re(H)4 (PNPR = (R2PCH2SiMe2)2N, R = iPr or cyclohexyl) reacts at 20 degrees C with 2 mol of cyclohexene to form equimolar cyclohexane and (PNPR)Re(H)2[=C(CH2)5]. This product is characterized by 1H, 13C, and 31P NMR and by X-ray diffraction as having one CH2 hydrogen (from a carbon located beta to Re) donating to the metal ("agostic CH"). This interaction occurs in preference to PNPR amide nitrogen pi-donation. DFT calculations confirm this agostic interaction, and show that the (PNPR)Re(H)2 fragment indeed reverses the greater stability of free olefin vs free carbene.

A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand. Publishing Authors By Initials

OV Ozerov,LA Watson,M Pink,KG Caulton,

For similar abstracts research abstracts see: abstracts research

PUBMED ID PMID:

MEDLINE DATE:

A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of the American Chemical Society

VOLUME: 125

Page Numbers: 9604-5

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 13

MONTH: Aug

YEAR: 2003

A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 7503056

A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand. Keywords Mesh Terms:

KEYWORDS:

MESH TERMS:

Chemical & Substance for Abstract: A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand. Information

Substance Name:

Registry Number:

Grant and Affiliation Information for A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand.

AFFILIATION: Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.

Country: United States

AGENCY:

GRANT:

ACRONYM:

MEDLINETA: J Am Chem Soc

REFSOURCE:

DATABASENAME:

ACCESSION NUMBER:

Number Hits: 0

A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand Related Publications

• A facile approach to a d4 RuN: moiety.
• A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand.
• Exceptionally facile CO addition to a saturated ruthenium complex.
• Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo.
• Four-coordinate, planar RuII. A triplet state as a response to a 14-valence electron configuration.
• Influence of the d-Electron Count on CO Binding by Three-Coordinate [((t)Bu(2)PCH(2)SiMe(2))(2)N]Fe, -Co, and -Ni.
• Influence of the metal orbital occupancy and principal quantum number on organoazide (RN3) conversion to transition-metal imide complexes.
• Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh.
• Multifunctional behavior by a Bis-(phosphinimino)methanide ligand: eta 2- vs eta 3-coordination vs Bronsted basicity.
• N2 provides insight into the mechanism of H-C(sp3) bond cleavage.
• Nitrogen-Ligated Iron Complexes: Photolytic Approach to the FeN(+) Moiety.
• O/C Bond Cleavage of CO2 by Ni(I).
• Radical (NO) and nonradical (N(2)O) reagents convert a ruthenium(IV) nitride to the same nitrosyl complex.
• Redox chemistry of the triplet complex (PNP)Co(I).
• Reducing power of three-coordinate cobalt(I).
• Spin State, Structure, and Reactivity of Terminal Oxo and Dioxygen Complexes of the (PNP)Rh Moiety.
• The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit.
• Three-coordinate Co(I) provides access to unsaturated dihydrido-Co(III) and seven-coordinate Co(V).
• [(tBu2PCH2SiMe2)2N]RuCH3: the origin of extremely facile, double H-C(sp3) activation generating a "hydrido-carbene" complex.