Crystal structures of [Rh(η5-C5H5)(C3S5)] and [Rh(η5-C5Me5)(C3S5)]2 and properties of their oxidized species

Reactivity and electrochemical behavior of ruthenium dithiolene complexes with coordinatively unsaturated metal centers: cycloaddition and dimerization reactions

“…The molar ratio of complexes 1a and 1a 0 was 20:1 (30°C in CDCl 3 ). The proposed structure of dimer 1a 0 is the structure dimerized by a sulfide coordination (Scheme 4); such a structure is suggested by two different 1 [18] have been reported in X-ray structure studies. In addition, Mashima et al [14] have reported the dimer of ruthenium dithiolene complexes containing 1,2-benzenedithiolate ligand [(arene)Ru(S 2 C 6 H 4 )] (arene = C 6 H 6 , C 6 H 4 (Me)(iPr)).…”

Rare monomeric structure of CpRh(III) dithiolene complex: Combined ESR and electronic absorption studies on electrochemically generated Rh(II) species

“…One other interest for this work is observation of rare monomeric [CpRh(dithiolene)] complex at solid state because they are almost dimeric as follows (Chart 1): [Cp * Rh(mnt)] 2 [22], [Cp * Rh(bdt)] 2 (bdt = benzene-1,2-dithiolate) [23] and [Cp * Rh-(dmit)] 2 (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) [24]. According to our literature survey, [Cp * (or Cp)Rh(dithiolene)] complexes are easy to dimerize in the crystals compared with the other [Cp * (or Cp)M(dithiolene)] (M = Co [7b], Ir [25] and Ni [10]) complexes.…”

“…In fact, monomeric complexes have been mostly reported except for the dimeric [CpCo(bdt)] 2 , which can monomerize at 150°C in the crystal [26]. The only example of the monomeric Rh complex is the [CpRh(dmit)] but its ESR study of the reduced species has not been reported [24]. Here we report the rare monomeric structure of [CpRh III (mnt)], its electrochemical behavior with CV and OTTLE techniques, and in situ ESR study of the electrochemically generated Rh(II) species.…”

“…1. The selected bond lengths, and bond angles of 1 are summarized in Table 1, together with those of the monomeric [CpRh(dmit)] and dimeric [Cp * Rh(dmit)] 2 [24]. Complex 1 crystallized in the monoclinic crystal system with space group C2/c, and 1 was isostructural to the monomeric [CpCo(mnt)] [30] Complex 1 has a typical two-legged piano-stool geometry because the Cp/RhS 2 dihedral angle is 90.139°, although the early reported dimeric [Cp * Rh(dithiolene)] 2 complexes have three-legged ones with Cp * /RhS 2 dihedral angle = ca.…”

“…Complex 1 crystallized in the monoclinic crystal system with space group C2/c, and 1 was isostructural to the monomeric [CpCo(mnt)] [30] Complex 1 has a typical two-legged piano-stool geometry because the Cp/RhS 2 dihedral angle is 90.139°, although the early reported dimeric [Cp * Rh(dithiolene)] 2 complexes have three-legged ones with Cp * /RhS 2 dihedral angle = ca. 50° [22][23][24] (5) and 2.3571(6) Å). One reason for the shorten Rh-S distance of 1 is strong p-electron donation from S to Rh [31], because the monomeric complex is coordinatively unsaturated with 16-electron metal center, although the dimeric one is coordinatively saturated with 18-electron complex.…”