Metal carbonyl clusters of groups 8-10: synthesis and catalysis.

In this review article, we discuss advances in the chemistry of metal carbonyl clusters (MCCs) spanning the last three decades, with an emphasis on the more recent reports and those involving groups 8-10 elements. Synthetic methods have advanced and been refined, leading to higher-nuclearity clusters and a wider array of structures and nuclearities. Our understanding of the electronic structure in MCCs has advanced to a point where molecular chemistry tools and other advanced tools can probe their properties at a level of detail that surpasses that possible with other nanomaterials and solid-state materials. MCCs therefore advance our understanding of structure-property-reactivity correlations in other higher-nuclearity materials. With respect to catalysis, this article focuses only on homogeneous applications, but it includes both thermally and electrochemically driven catalysis. Applications in thermally driven catalysis have found success where the reaction conditions stabilise the compounds toward loss of CO. In more recent years, MCCs, which exhibit delocalised bonding and possess many electron-withdrawing CO ligands, have emerged as very stable and effective for reductive electrocatalysis reactions since reduction often strengthens M-C(O) bonds and since room-temperature reaction conditions are sufficient for driving the electrocatalysis.

Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers.

Photoredox catalysis has emerged as a powerful strategy in synthetic organic chemistry, but substrates that are difficult to reduce either require complex reaction conditions or are not amenable at all to photoredox transformations. In this work, we show that strong bis-cyclometalated iridium photoreductants with electron-rich ß-diketiminate (NacNac) ancillary ligands enable high-yielding photoredox transformations of challenging substrates with very simple reaction conditions that require only a single sacrificial reagent. Using blue or green visible-light activation we demonstrate a variety of reactions, which include hydrodehalogenation, cyclization, intramolecular radical addition, and prenylation via radical-mediated pathways, with optimized conditions that only require the photocatalyst and a sacrificial reductant/hydrogen atom donor. Many of these reactions involve organobromide and organochloride substrates which in the past have had limited utility in photoredox catalysis. This work paves the way for the continued expansion of the substrate scope in photoredox catalysis.

Potent Bis-Cyclometalated Iridium Photoreductants with ß-Diketiminate Ancillary Ligands.

In this work, we outline a strategy to prepare a class of improved visible-light photosensitizers. Bis-cyclometalated iridium complexes with electron-rich ß-diketiminate (NacNac) ancillary ligands are demonstrated to be potent excited-state electron donors. Evaluation of the photophysical and electrochemical properties establishes the excited-state redox potentials of the complexes, and Stern-Volmer quenching experiments inform on the kinetics of photoinduced electron transfer to the model substrates methyl viologen (MV2+) and benzophenone (BP). Compared to fac-Ir(ppy)3 (ppy = 2-phenylpyridine), widely regarded as a state-of-the-art photoreductant, the complexes we describe have excited-state redox potentials that are more potent by 300-400 mV and rates for photoinduced electron transfer that are accelerated by as much as a factor of 3. These complexes emerge as promising targets for application in photocatalytic reactions and other photochemical processes.