The nickel hydride dimer [(dippe)NiH]2 (1) was found to react with a variety of organosulfur substrates under mild conditions leading to C−S bond insertion adducts. The transition-metal insertions ...

Modeling the Hydrodesulfurization Reaction at Nickel. Unusual Reactivity of Dibenzothiophenes Relative to Thiophene and Benzothiophene

Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

Chemical transformations that result in either the formation or cleavage of carbon–heteroatom bonds are among the most important processes in the chemical sciences. Herein, we present a review on the reactivity of well-defined, late-transition metal complexes that result in the making and breaking of C–N, C–O and C–S bonds via fundamental organometallic reactions, i.e. oxidative addition, reductive elimination, insertion and elimination reactions. When appropriate, emphasis is placed on structural and spectroscopic characterization techniques, as well as mechanistic data.

Recent advances in well-defined, late transition metal complexes that make and/or break C–N, C–O and C–S bonds

Over the past 20 years, substantial progress has been made in the understanding of the activation of C-H and other strong bonds by reactive metal complexes in low oxidation states This paper will present an overview of the use of pentamethylcyclopentadienyl and trispyrazolylborate rhodium complexes for the activation of arene and alkane C -H bonds Insights into bond strengths, kinetic and thermodynamic selectivities, and the nature of the intermediates involved will be reviewed The role of -2 arene complexes will be shown to be critical to the C-H activation reactions Some information about the fleeting alkane U-complexes will also be presented In addition, use of these complexes with thiophenes has shown the ability to cleave C -S bonds Mechanistic information has been obtained indicating coordination through sulfur prior to cleavage Relevant examples of nickel-based C -S cleavage will also be given

On the nature of carbon-hydrogen bond activation at rhodium and related reactions.

Interpretation and comparison of the vibrational spectra of organometallic complexes containing thiophene ligands with IR spectra of adsorbed thiophene on sulfided Mo/Al2O3 catalysts have permitted a definitive assignment of the adsorption mode of the surface-bonded thiophene. Infrared and Raman spectra were acquired for three organometallic complexes:  (η5-C5D5)Re(CO)2(η1(S)-C4H4S), (η5-C4H4S)Cr(CO)3, and [(η5-C4H4S)Mn(CO)3]BF4. The vibrational properties of η1(S)- and η5-coordinated thiophene were further investigated through normal-mode analyses of the IR spectra of thiophene coordinated in (η5-C4H4S)Cr(CO)3 and (η5-C5D5)Re(CO)2(η1(S)-C4H4S). Perturbations among the force constants of a gas-phase thiophene model, consistent with the structure of η1(S)- and η5-coordinated thiophene ligands, gave rise to respective thiophene force fields that allowed for the accurate determination of the IR spectra of thiophene coordinated in the Cr and Re complexes. Spectral shifts observed for the IR spectrum of the η1...

Andy W. Myers

Papers

Homogeneus models of thiophene HDS reactions. Selectivity in thiophene CS cleavage and thiophene reactions with dinuclear metal complexes