First-row Transition Metal Systems Research Articles

Electrocatalytic formate and alcohol oxidation by hydride transfer at first-row transition metal complexes.

The electrocatalytic oxidation of carbon-based liquid fuels, such as formic acid and alcohols, has important applications for our renewable energy transition. Molecular electrocatalysts based on transition metal complexes provide the opportunity to explore the interplay between precise catalyst design and electrocatalytic activity. Recent advances have seen the development of first-row transition metal electrocatalysts for these transformations that operate via hydride transfer between the substrate and catalyst. In this Frontier article, we present the key contributions to this field and discuss the proposed mechanisms for each case. These studies also reveal the remaining challenges for formate and alcohol oxidation with first-row transition metal systems, for which we provide perspectives on future directions for next-generation electrocatalyst design.

Toward Highly Accurate Spin State Energetics in First-Row Transition Metal Complexes: A Combined CASPT2/CC Approach

In previous work on the performance of multiconfigurational second-order perturbation theory (CASPT2) in describing spin state energetics in first-row transition metal systems [ Pierloot et al. J. Chem. Theory Comput. 2017 , 13 , 537 - 553 ], we showed that standard CASPT2 works well for valence correlation but does not describe the metal semicore (3s3p) correlation effects accurately. This failure is partially responsible for the well-known bias toward high-spin states of CASPT2. In this paper, we expand our previous work and show that this bias could be partly removed with a combined CASPT2/CC approach: using high-quality CASPT2 with extensive correlation-consistent basis sets for valence correlation and low-cost CCSD(T) calculations with minimal basis sets for the metal semicore (3s3p) correlation effects. We demonstrate that this approach is efficient by studying the spin state energetics of a series of iron complexes modeling important intermediates in oxidative catalytic processes in chemistry and biochemistry. On the basis of a comparison with bare CCSD(T) results from this and previous work, the average error of the CASPT2/CC approach is estimated at around 2 kcal mol-1 in favor of high spin states.

CTM4DOC: electronic structure analysis from X-ray spectroscopy.

Two electronic structure descriptions, one based on orbitals and the other based on term symbols, have been implemented in a new Matlab-based program, CTM4DOC. The program includes a graphical user interface that allows the user to explore the dependence of details of electronic structure in transition metal systems, both in the ground and core-hole excited states, on intra-atomic electron-electron, crystal-field and charge-transfer interactions. The program can also track the evolution of electronic structure features as the crystal-field parameters are systematically varied, generating Tanabe-Sugano-type diagrams. Examples on first-row transition metal systems are presented and the implications on the interpretation of X-ray spectra and on the understanding of low-spin, high-spin and mixed-spin systems are discussed.

Accurate Computed Enthalpies of Spin Crossover in Iron and Cobalt Complexes

Despite their importance in many chemical processes, the relative energies of spin states of transition metal complexes have so far been haunted by large computational errors. By the use of six functionals, B3LYP, BP86, TPSS, TPSSh, M06, and M06L, this work studies nine complexes (seven with iron and two with cobalt) for which experimental enthalpies of spin crossover are available. It is shown that such enthalpies can be used as quantitative benchmarks of a functional's ability to balance electron correlation in both the involved states. TPSSh achieves an unprecedented mean absolute error of approximately 11 kJ/mol in spin transition energies, with the local functional M06L a distant second (25 kJ/mol). Other tested functionals give mean absolute errors of 40 kJ/mol or more. This work confirms earlier suggestions that 10% exact exchange is near-optimal for describing the electron correlation effects of first-row transition metal systems. Furthermore, it is shown that given an experimental structure of an iron complex, TPSSh can predict the electronic state corresponding to that experimental structure. We recommend this functional as current state-of-the-art for studying spin crossover and relative energies of close-lying electronic configurations in first-row transition metal systems.

Molecular and electronic structure of electron-transfer active main-group organometallics

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMolecular and electronic structure of electron-transfer active main-group organometallicsJens Baumgarten, Christian Bessenbacher, Wolfgang Kaim, and Thomas StahlCite this: J. Am. Chem. Soc. 1989, 111, 6, 2126–2131Publication Date (Print):March 1, 1989Publication History Published online1 May 2002Published inissue 1 March 1989https://doi.org/10.1021/ja00188a028RIGHTS & PERMISSIONSArticle Views281Altmetric-Citations28LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (715 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts