Organometallics Roundtable 2013–2014

Abstract

A panel of seventeen experts from academia, industry, and government laboratories share their thoughts on a variety of matters of importance to the readership of Organometallics. These include directions for the field and recent breakthroughs (illustrated with selected examples), the interface with green chemistry, the quest for reproducible experimental procedures, data and research integrity, laboratory safety, the preparation of coworkers for non-academic careers, and needs regarding instrumentation, infrastructure, shared facilities, and computational methods. A lively give and take is evident in the edited transcript, which continues a biennial tradition initiated in 2011.

Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides

“…The bidirectionality of many [FeFe]- and [NiFe]-H 2 ases has evolved not only from a biological need to both consume and dispense reducing equivalents, but also to operate in very narrow potential ranges and at low concentrations of H 2 and H +.6 Furthermore, for a H 2 -processing catalyst to be bidirectional, it follows that interconversion of H 2 and hydrides must be rapid and close to isoergic. 428 Such a transformation has been identified as a major challenge in organometallic chemistry, 429 and the viability of H 2 as an energy vector is reliant on both its efficient production and consumption. Electrocatalysis is certainly not the only means of H 2 processing, but it is notable that the reaction of H 2 and O 2 430 in fuel cells is potentially more efficient than traditional combustion, in which energy losses from the Carnot cycle are unavoidable.…”

Room temperature hydrophosphination using a simple iron salen pre-catalyst

“…3 Hydrophosphination (HP) offers the ideal P-C bond-forming process: the potential to be a 100% atom economic transformation with opportunities for regio-and stereocontrol, where molecular complexity can be rapidly accessed from simple, commercially available starting materials. 4,5 Whilst Platinum Group Metals (PGMs), early transition metals, lanthanides alkaline-and rare-earth metals have all 4 proved competent in catalyzing HP, it is of note that the use of base metals in this transformation is limited. 6,7 With this in mind, and driven by the major global efforts towards the development of sustainable chemical methodology, we sought to address these challenges through the use of iron, an appealing low cost, highly abundant, biocompatible and non-toxic alternative to the PGMs.…”

Aerobic Linear Allylic C–H Amination: Overcoming Benzoquinone Inhibition

“…Pd(OAc) 2 ] or weakly coordinating, oxidatively stable ligands such as bis-sulfoxide. 10 For allylic C—H acetoxylations and aminations under such conditions, the slow electron transfer directly between Pd(0) and O 2 relative to the rapid formation of palladium black via precipitation of palladium metal is thought to result in deleterious olefin isomerization processes and contribute to the requirement for high catalyst loadings. 11–14 While aerobic Pd(II)-catalyzed linear allylic C—H aminations have been reported, their utility is limited by requirements such as excess alkene (e.g.…”