Metal-only Lewis Pairs of Rhodium with s, p and d-Block Metals
| Autor: | Jesús Campos, María M. Alcaide, Sonia Bajo, Macarena G. Alférez, Joaquín López-Serrano |
|---|---|
| Přispěvatelé: | Universidad de Sevilla. Departamento de Química Inorgánica, European Research Council (ERC), Ministerio de Economía y Competitividad (MINECO). España |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Organometallic Chemistry
bimetallic compounds metal–metal bond Supramolecular chemistry Ionic bonding chemistry.chemical_element 010402 general chemistry 01 natural sciences Catalysis Rhodium Metal Bimetallic strip dative bond metal-only Lewis pair Full Paper 010405 organic chemistry Chemistry Organic Chemistry General Chemistry Nuclear magnetic resonance spectroscopy rhodium NMR Full Papers Block (periodic table) 3. Good health 0104 chemical sciences Crystallography Main group element visual_art visual_art.visual_art_medium |
| Zdroj: | Chemistry (Weinheim an Der Bergstrasse, Germany) Digital.CSIC. Repositorio Institucional del CSIC instname Chemistry – A European Journal |
| Popis: | Metal‐only Lewis pairs (MOLPs) in which the two metal fragments are solely connected by a dative M→M bond represent privileged architectures to acquire fundamental understanding of bimetallic bonding. This has important implications in many catalytic processes or supramolecular systems that rely on synergistic effects between two metals. However, a systematic experimental/computational approach on a well‐defined class of compounds is lacking. Here we report a family of MOLPs constructed around the RhI precursor [(η 5‐C5Me5)Rh(PMe3)2] (1) with a series of s, p and d‐block metals, mostly from the main group elements, and investigate their bonding by computational means. Among the new MOLPs, we have structurally characterized those formed by dative bonding between 1 and MgMeBr, AlMe3, GeCl2, SnCl2, ZnMe2 and Zn(C6F5)2, as well as spectroscopically identified the ones resulting from coordination to MBArF (M=Na, Li; BArF −=[B(C6H2‐3,5‐(CF3)2)4]−) and CuCl. Some of these compounds represent unique examples of bimetallic structures, such as the first unambiguous cases of Rh→Mg dative bonding or base‐free rhodium bound germylene and stannylene species. Multinuclear NMR spectroscopy, including 103Rh NMR, is used to probe the formation of Rh→M bonds. A comprehensive theoretical analysis of those provides clear trends. As anticipated, greater bond covalency is found for the more electronegative acids, whereas ionic character dominates for the least electronegative nuclei, though some degree of electron sharing is identified in all cases. A new family is born: We report a family of metal‐only Lewis pairs based on the basic RhI compound [(η 5‐C5Me5)Rh(PMe3)2] with a series of s, p and d‐block metal fragments. We provide the structural characterization of those based on Ge, Sn, Al and Mg, as well as two RhI→ZnII adducts. Our combined experimental/computational approach provides valuable insights into the Rh→M dative bonding. |
| Databáze: | OpenAIRE |
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