Electromeric Rhodium Radical Complexes

Puschmann, Florian Frank; Harmer, Jeffrey; Stein, Daniel; Rüegger, Heinz; Bruin, Bas de

doi:10.1002/ange.200903201

Cited by 17 publications

(7 citation statements)

References 29 publications

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“…The DFT calculated EPR parameters of 2 are in good agreement with the experimental parameters (Table ). In contrast to all the previously reported formal rhodium(0) complexes, complex 2 is a genuine metal‐centered radical.…”

Section: Methodscontrasting

confidence: 84%

“…Those of Rh 0 have been characterized and many of them fully studied by EPR spectroscopy and DFT methods . Interestingly, they are all highly delocalized radicals, with the exception of one metal‐centered radical, [Rh(trop 2 PPh)(PPh 3 )], [ρ(Rh) 58 %], which is in electromeric equilibrium with the delocalized radical . In any case, isolated compounds of rhodium in the oxidation states 0 and −1 are rare and their chemistry is underdeveloped.…”

Section: Methodsmentioning

confidence: 99%

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Three‐Coordinate Rhodium Complexes in Low Oxidation States

Varela‐Izquierdo

López

Bruin

et al. 2020

Chemistry A European J

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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.

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Section: Methodscontrasting

confidence: 84%

Section: Methodsmentioning

confidence: 99%

Three‐Coordinate Rhodium Complexes in Low Oxidation States

Varela‐Izquierdo

López

Bruin

et al. 2020

Chemistry A European J

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“…Hence, simple ligand displacement leads to a completely different electronic structure, which is somewhat comparable to the electromeric forms of a recently reported rhodium(0) species. [15] The observed redox or valence isomerism is not the only type of isomerism that relates 3a and 3b (Scheme 1). On going from 3a to 3b, a marked shortening of the rhodiumiridium bond length (ca.…”

Section: Resultsmentioning

confidence: 97%

Snapshots of a Reversible Metal–Ligand Two‐Electron Transfer Step Involving Compounds Related by Multiple Types of Isomerism

et al. 2011

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An unusual and very fast equilibrium between two isomers, [(cod)Rh–I{(bpa – 2H)0}IrI(cod)][rlhar2][(cod)RhI{(bpa – 2H)2–}IrI(cod)], which simultaneously display multiple types of isomerism: ligand–metal redox (electromerism), linkage, bond‐stretch and ring‐slippage isomerism, has been studied by NMR spectroscopy and DFT calculations. Both isomers have been isolated by making rational use of their thermodynamic parameters (ΔH° = +1.93 kcal mol–1; ΔS° = +7.8 cal mol–1 K–1), and have been characterized by X‐ray diffraction methods. The equilibrium that involves a two‐electron exchange between a redox noninnocent ligand, which transforms from a deprotonated amido form into an imine, and a metal that is reduced, could elucidate a thus far obscure step in the oxidative dehydrogenation of amines to imines.

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“…Noticeably, some of these complexes exhibit very rich non-conventional chemical reactivity, [3] including dinuclear CÀH bond activation reactions, [4] and unusual electromeric rhodium radical complexes. [5] The above mentioned examples provide invaluable information on the parameters that control the electronic structure from a particular geometry and vice versa. [2] Some of these parameters are the ligand topology and bonding effects, such as strong pdonation, as verified by the unique square-planar (SP) iridium(II) and iridium(III) complexes based on pincer ligands, [6] or by the pseudotetrahedral metal environments created by the high-field scorpionate ligands, [PhB(CH 2 PR 2 ) 3 ] À .…”

mentioning

confidence: 99%