Three-Coordinate Rhodium Complexes in Low Oxidation States
| Autor: | Cristina Tejel, Miguel A. Ciriano, José A. López, Bas de Bruin, Victor Varela-Izquierdo |
|---|---|
| Přispěvatelé: | Ministerio de Economía y Competitividad (España), European Commission, Netherlands Organization for Scientific Research, Gobierno de Aragón, Homogeneous and Supramolecular Catalysis (HIMS, FNWI) |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
NHC ligands
chemistry.chemical_element Trigonal pyramidal molecular geometry 010402 general chemistry 01 natural sciences Medicinal chemistry Chloride Catalysis Rhodium Metal Paramagnetism Nucleophile medicine Tri-coordinate low-valent Metal–metal bond 010405 organic chemistry Ligand Organic Chemistry General Chemistry 0104 chemical sciences Unpaired electron chemistry visual_art visual_art.visual_art_medium medicine.drug |
| Zdroj: | Chemistry-A European Journal, 26(15), 3270-3274. Wiley-VCH Verlag Digital.CSIC. Repositorio Institucional del CSIC instname |
| ISSN: | 0947-6539 |
| Popis: | The isolation of simultaneously low‐coordinate and low‐valent compounds is a timeless challenge for preparative chemists. This work showcases the preparation and full characterization of tri‐coordinate rhodium(‐I) and rhodium(0) complexes as well as a rare rhodium(I) complex. Reduction of [{Rh(μ‐Cl)(IPr)(dvtms)}2] (1 , IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolyl‐2‐ylidene; dvtms=divinyltetramethyldisiloxane) with KC8 gave the trigonal complexes K[Rh(IPr)(dvtms)] and [Rh(IPr)(dvtms)], whereas the cation [Rh(IPr)(dvtms)]+ results from their oxidation or by abstraction of chloride from 1 with silver salts. The paramagnetic Rh0 complex is a unique fully metal‐centered radical with the unpaired electron in the dz2 orbital. The Rh(‐I) complex reacts with PPh3 with replacement of the NHC ligand, and behaves as a nucleophile, which upon reaction with [AuCl(PPh3)] generates the trigonal pyramidal complex [(IPr)(dvtms)Rh‐Au(PPh3)] with a metal–metal bond between two d10 metal centers. The generous financial support from MINECO/FEDER/AGE (CTQ2017‐83421‐P, C.T.), Gobierno de Aragón/FEDER (GA/FEDER, Inorganic Molecular Architecture Group E08_17R; C.T.) and the Netherlands Organization for Scientific Research (NWO) (TOP Grant 716.015.001, BdB) is gratefully acknowledged. V.V.‐I. thanks MINECO/FEDER for a FPI fellowship. |
| Databáze: | OpenAIRE |
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