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• W2159291597 abstract "d or s regime? That is the question! A catalyst's orbital electronic regime (see illustration) and bite-angle flexibility are proposed as unifying concepts that serve a more rational design of catalysts. They emerge from quantum-chemical activation strain analyses of 72 different d10-M(L)n model catalyst mediated CH bond-activation reactions. Our aim is to understand the electronic and steric factors that determine the activity and selectivity of transition-metal catalysts for cross-coupling reactions. To this end, we have used the activation strain model to quantum-chemically analyze the activity of catalyst complexes d10-M(L)n toward methane CH oxidative addition. We studied the effect of varying the metal center M along the nine d10 metal centers of Groups 9, 10, and 11 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+), and, for completeness, included variation from uncoordinated to mono- to bisligated systems (n=0, 1, 2), for the ligands L=NH3, PH3, and CO. Three concepts emerge from our activation strain analyses: 1) bite-angle flexibility, 2) d-regime catalysts, and 3) s-regime catalysts. These concepts reveal new ways of tuning a catalyst’s activity. Interestingly, the flexibility of a catalyst complex, that is, its ability to adopt a bent L-M-L geometry, is shown to be decisive for its activity, not the bite angle as such. Furthermore, the effect of ligands on the catalyst’s activity is totally different, sometimes even opposite, depending on the electronic regime (d or s) of the d10-M(L)n complex. Our findings therefore constitute new tools for a more rational design of catalysts. Ons doel is het begrijpen van de elektronische en sterische factoren die bepalend zijn voor de activiteit en selectiviteit van overgangsmetaalkatalysatoren voor koppelingsreacties. Hiervoor hebben wij, met behulp van het activeringsspanningsmodel, de activiteit van verschillende d10-M(L)n katalysatorcomplexen in de oxidatieve additie van de CH binding van methaan quantumchemisch geanalyseerd. Wij hebben de effecten bestudeerd van het variëren van het metaalcentrum M langs alle negen d10 metaalcentra van groep 9, 10 en 11 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+) voor zowel de ongecoördineerde metalen alsmede de enkel- en tweevoudig gecoördineerde complexen (n=0, 1, 2), met NH3, PH3 en CO als liganden. Uit onze analyses komen drie concepten naar voren: 1) de ‘bite-angle flexibiliteit′; 2) d-regime katalysatoren; en 3) s-regime katalysatoren. Deze concepten ontsluiten nieuwe wegen om de activiteit van katalysatoren nauwkeurig af te stellen. Een belangrijk nieuw inzicht is dat de activiteit van een katalysator niet zo zeer wordt bepaald door de waarde van de L-M-L hoek, maar vooral door het gemak waarmee deze hoek tijdens een reactie kan buigen. Tevens tonen onze analyses aan dat het effect van een ligand bepaald wordt door het elektronische regime (d of s) van het d10-M(L)n complex en, afhankelijk hiervan, zelfs volkomen kan omkeren. Onze vindingen vormen nieuwe gereedschappen voor het rationeler ontwerpen van katalysatoren. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article." @default.
• W2159291597 created "2016-06-24" @default.
• W2159291597 creator A5036767858 @default.
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• W2159291597 date "2014-07-31" @default.
• W2159291597 modified "2023-09-26" @default.
• W2159291597 title "New Concepts for Designing d¹⁰-M(L)_<i>n</i>Catalysts: d Regime, s Regime and Intrinsic Bite-Angle Flexibility" @default.
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• W2159291597 doi "https://doi.org/10.1002/chem.201403237" @default.
• W2159291597 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/25081592" @default.
• W2159291597 hasPublicationYear "2014" @default.
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