Synthesis, structure, and reactivity of thienyl-, benzothienyl-, and selenylcarbene complexes of rhenium. A new mechanicm of H/D exchange during hydrodesulfurization

Journal Article · Wed Nov 30 23:00:00 EST 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00024a064· OSTI ID:6730671

White, C J; Angelici, R J ^[1]

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1. Iowa State Univ., Ames, IA (United States)

A series of [eta][sup 1](E)-coordinated (E = S or Se) thiophene, benzo[b]thiophene and selenophene complexes [Cp(NO)(PPh[sub 3])Re([eta][sup 1](E)-L)][sup +], Cp = C[sub 5]H[sub 5], L = thiophene (T), 2-methylthiophene (2-MeT), 2,5-dimethylthiophene (2,5-Me[sub 2]T), benzo[b]thiophene (BT), 3-methylbenzo[b]thiophene (3-MeBT), selenophene (Sel), 2-methylselenophene (2-MeSel), and 2,5-dimethylselenophene (2,5-Me[sub 2]Sel) are prepared by the reaction of [Cp(NO)(PPh[sub 3])Re(ClC[sub 6]H[sub 5])][sup +] with the appropriate ligand. The T, 2-MeT, BT, 3-MeBT, Sel, 2-MeSel complexes are deprotonated at C(2) by strong, non-nucleophilic bases to give the neutral Cp(NO)(PPh[sub 3])Re(2-L-yl) complexes, where 2-L-yl = 2-thienyl (2-Tyl), 2-5(methylthienyl) (2-(5-MeTyl), 2[minus]benzothienyl (2-BTyl), 2-(3-methylbenzothienyl) (2-3-MeBTyl)), 2-selenyl (2-Selyl), and 2-(5-methylselenyl) (2-5-MeSelyl). The pK[sub a] of the base required to effect this deprotonation increases with the L ligand in the complex in the following order: Sel < T < BT. The 2-Tyl, 2-BTyl and 2-Selyl complexes react with either HBF[sub 4][center dot]Et[sub 2]O or HO[sub 3]SCF[sub 3] at [minus]42[degrees]C to give the corresponding carbene complexes [Cp(NO)(PPh[sub 3])Re(2-L-ylcarbene)][sup +] resulting from protonation at C(3). 43 refs., 2 figs., 5 tabs.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6730671
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:12; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400101 -- Activation
Nuclear Reaction
Radiometric &amp; Radiochemical Procedures
400102 -- Chemical &amp; Spectral Procedures
400201* -- Chemical &amp; Physicochemical Properties
CHEMICAL BONDS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
DATA
DESULFURIZATION
DEUTERIUM
DIFFRACTION
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
INFRARED SPECTRA
ISOTOPES
ISOTOPIC EXCHANGE
LIGANDS
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RESONANCE
RHENIUM COMPLEXES
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION