2009
DOI: 10.1002/anie.200903201
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Electromeric Rhodium Radical Complexes

Abstract: Electromers are species with significantly different electronic but only slightly different geometrical structures, whereby each species corresponds to a local minimum on the energy hypersurface.[1a-c] Although they have been discussed several times in the literature, direct observation of "electroisomers"-the synonyms "redox isomers" or "valence isomers" are likewise used-is rare.[2] Paramagnetic transition-metal complexes are ideally suited to the study of this phenomenon, and the localization of the spin on… Show more

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Cited by 34 publications
(27 citation statements)
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“…In fact, SH and TP structures can be envisaged as derived formally from a trigonal bipyramid (TBPY) geometry lacking either one equatorial or one axial ligand, respectively. Noticeably, some of these complexes exhibit very rich non‐conventional chemical reactivity,3 including dinuclear CH 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.…”
Section: Methodsmentioning
confidence: 99%
“…In fact, SH and TP structures can be envisaged as derived formally from a trigonal bipyramid (TBPY) geometry lacking either one equatorial or one axial ligand, respectively. Noticeably, some of these complexes exhibit very rich non‐conventional chemical reactivity,3 including dinuclear CH 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.…”
Section: Methodsmentioning
confidence: 99%
“…7 In absence of additional PPh 3 , we observed quantitative and selective conversion of the radical species to the diamagnetic Rh I complexes 2 and 3 in a 1:1 ratio within 10 h at room temperature (Scheme 2). 8 The benzo-1-rhoda-2-phosphacyclobutane complex 2 is ortho-metalated at one of the aromatic rings of PPh 3 , while the axial hydride complex 3 contains an unmodified PPh 3 ligand.…”
mentioning
confidence: 91%
“…In certain cases, subtle changes to the system through variation of the ligand field, or temperature is sufficient to shift the oxidation locus. [5, 6] Recent work in this area has focused on bis(salicylidene)diamine complexes 1-3 (Scheme 1). [6-11] The one-electron oxidized Ni derivatives exist in the ligand radical form Ni II (L •- ) in solution and the solid state, however the addition of exogenous ligands to Ni II (L •- ) in solution results in a shift in the oxidation locus to the Ni III (L 2- ) form.…”
mentioning
confidence: 99%