The use of multimetallic complexes is a rapidly advancing route to enhance catalyst performance in the ring-opening polymerization of cyclic esters and ethers. Multimetallic catalysts often outperform their monometallic analogues in terms of reactivity and/or polymerization control, and these improvements are typically attributed to "multimetallic cooperativity". Yet the origins of multimetallic cooperativity often remain unclear. This review explores the key factors underpinning multimetallic cooperativity, including metal-metal distances, the flexibility, electronics and conformation of the ligand framework, and the coordination environment of the metal centers. Emerging trends are discussed to provide insights into why cooperativity occurs and how to harness cooperativity for the development of highly efficient multimetallic catalysts.
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http://dx.doi.org/10.1021/acscatal.3c05103 | DOI Listing |
Inorg Chem
November 2024
Department of Chemistry, University of Calcutta, Kolkata 700009, West Bengal, India.
Chem Rec
November 2024
Interdisciplinary Research Center for Hydrogen Technologies and Carbon Management (IRC-HTCM), King Fahd University of Petroleum and Minerals (KFUPM), Dhahran, -31261, Saudi Arabia.
Angew Chem Int Ed Engl
December 2024
Department of Chemistry and Biochemistry, The Ohio State University, 100 W. 18th Ave. 3109 Newman and Wolfrom, Columbus, Ohio, 43210, United States.
Hydrogenations are fundamentally and industrially important reactions that are atom economical paths to synthesize value-added products from feedstock chemicals. The cooperative effects of two or more metal centers in multimetallic active sites is a successful strategy to activate small molecules and facilitate catalytic reactions, and this strategy has been recently applied to catalytic hydrogenation reactions. Furthermore, heterobimetallic complexes have been well-documented to provide novel reaction pathways and improved selectivity, compared to their homo-bimetallic and monometallic analogues.
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August 2024
Los Alamos National Laboratory (LANL) P. O. Box 1663, Los Alamos New Mexico 87545 USA
Recent advances enabled the discovery of heterometallic molecules for many metals: main group, d-block, lanthanides, and some actinides (U, Th). These complexes have at least two different metals joined by bridging ligands or by direct metal-metal bonding interactions. They are attractive because they can enable chemical cooperativity between metals from different parts of the periodic table.
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June 2024
Department of Chemistry, Chemical Sciences Division, Lawrence Berkeley National Laboratory, University of California Berkeley California 94720 USA
Transition metal multimetallic complexes have seen intense study due to their unique bonding and potential for cooperative reactivity, but actinide-transition metal (An-TM) species are far less understood. We have synthesized uranium- and thorium-osmium heterometallic polyhydride complexes in order to study An-Os bonding and investigate the reactivity of An-Os interactions. Computational studies suggest the presence of a significant bonding interaction between the actinide center and the four coordinated osmium centers supported by bridging hydrides.
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