Electrochemical characterization of a novel rhodium(II) dimer, Rh2(ONHCCF3)4

Kadish, Karl M.; Lançon, D.; Dennis, A. M.; Bear, John L.

doi:10.1021/ic00138a015

Cited by 27 publications

(11 citation statements)

References 3 publications

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“…The geometry about each of the metal centres is that of a distorted octahedron with the angles between adjacent atoms in the metal co-ordination (C5H,N),ICPF612 3. 7) 1495 (6) 971( 5) 17(5) -377 (5) sphere falling in the range 81.2(1)-97.0(1)". The smallest of these angles is that formed by the 'bite' of the phenanthroline ligands, while the largest occur between Rh-Rh and Rh-N(phen) vectors.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, characterisation and crystal structure of a dirhodium(II) compound with two bridging trifluoroacetamidate ligands

Daniels¹,

Mehmet²,

Tocher³

1991

J. Chem. Soc., Dalton Trans.

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Section: Resultsmentioning

confidence: 99%

Synthesis, characterisation and crystal structure of a dirhodium(II) compound with two bridging trifluoroacetamidate ligands

Daniels¹,

Mehmet²,

Tocher³

1991

J. Chem. Soc., Dalton Trans.

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“…The first isolation of a tetrakis(carboxylato) compound of the type Rh 2 (O 2 CR) 4 was described in 1960, and this was followed over the years by the synthesis of a large number of other dirhodium complexes with tetracarboxylate type structures, − many of which were also characterized as to their structural, electrochemical, and/or spectroscopic properties. The tetrabridged dirhodium complexes investigated to date can be classified as “monomeric” 1,5-25 or, in some cases, as “polymeric” 2-4 species, but little is known as to how the electronic and spectroscopic properties of these compounds might be altered when the two dirhodium complexes are axially linked to each other via a rigid spacer.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Electrochemistry, and Spectroscopic Characterization of Bis-dirhodium Complexes Linked by Axial Ligands

Bear

Han

et al. 2001

Inorg. Chem.

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The synthesis and electrochemical and spectroscopic properties of bis-dirhodium complexes containing ap or dpf bridging ligands, (ap)(4)Rh(2)(C triple bond C)(2)Rh(2)(ap)(4) (2) and (dpf)(4)Rh(2)(CNC(6)H(4)NC)Rh(2)(dpf)(4) (4), were investigated (where ap and dpf are the 2-anilinopyridinate and N,N'-diphenylformamidinate ions, respectively). The related "simple" dirhodium species, (ap)(4)Rh(2)(C triple bond C)(2)Si(CH(3))(3) (1) and (dpf)(4)Rh(2)(CNC(6)H(5)) (3), with the same set of bridging ligands were also synthesized and their properties compared to those of the analogous bis-dirhodium complexes. Compound 1 was obtained by mixing (ap)(4)Rh(2)Cl and Li(C triple bond C)(2)Si(CH(3))(3) in refluxing THF for 16 h under vacuum while compound 2 was prepared by a reaction between (ap)(4)Rh(2)(C triple bond C)(2)Li and (ap)(4)Rh(2)Cl under similar conditions. The reaction between (CF(3)COO)(4)Rh(2) and molten Hdpf under vacuum for 24 h leads to the generation of compound 3 with a yield of 65%. The red-orange compound 4 was obtained upon addition of 0.5 equiv of CNC(6)H(4)NC at room temperature to a CH(2)Cl(2) solution containing (dpf)(4)Rh(2) which was synthesized according to a method described previously in the literature. Compound 1 crystallizes in the triclinic space group P1, with a = 10.164(3) A, b = 13.881(3) A, c = 18.805(4) A, alpha = 73.55(2) degrees, beta = 77.89(2) degrees, gamma = 84.85(2) degrees, and Z = 2. Crystals of 2 were not good enough to collect adequate data for X-ray analysis, but the identity of this compound was confirmed, along with its P1; space group. Crystals of 3 and 4 belong to the monoclinic, P2(1)/c space group and the triclinic, P1; space group, respectively, with a = 13.5254(5) A, b = 13.7387(4) A, c = 27.2011(12) A, beta = 102.637(2) degrees, and Z = 4 for 3 and a = 13.866(8) A, b = 14.756(7) A, c = 15.008(6) A, alpha = 79.91(3) degrees, beta = 87.72(4) degrees, gamma = 89.19(4) degrees, and Z = 1 for 4. Compound 1 exhibits a single reversible oxidation at E(1/2) = 0.66 V and a single reversible reduction at E(1/2) = -0.44 V vs SCE in THF, 0.2 M TBAP. Both processes involve a one-electron transfer. Compound 2 undergoes a reversible oxidation at E(1/2) = 0.60 V and two separate one-electron-transfer reductions at E(1/2) = -0.52 and -0.65 V in THF, 0.2 M TBAP. The oxidation involves two overlapped one-electron-transfer processes. Compounds 3 and 4 undergo two reversible oxidations in CH(2)Cl(2), 0.1 M TBAP located at E(1/2) = 0.23 and 1.22 V (3) or 0.22 and 1.20 V (4). Each redox reaction of 3 involves a one-electron-transfer step while each redox reaction of 4 involves two overlapping one-electron transfers. Compound 2 shows interaction between the two dirhodium cores upon reduction, while 4 gives no evidence of electronic interaction between the two dirhodium units during either reduction or oxidation. An ESR signal with axial symmetry was obtained for the neutral compounds 1 and 2, and a similar spectrum was obtained for the singly oxidized products of compounds 3 and 4, thus sug...

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“…Addition of a MeOH solution containing [Pt 2 (OPiv) 2 (NH 3 ) 4 ]-(ClO 4 ) 2 ·PivOH to a MeOH suspension of [Rh 2 (acam)4 ] resulted in a gradual colour change from bluish-purple to reddishpurple.Fig. The spectrum of [Rh 2 (acam) 4 ] shows two bands at 370 and 558 nm attributed to π* → σ*(Rh-O) and π* → σ* transitions, respectively 44,45. The spectrum of [Rh 2 (acam) 4 ] shows two bands at 370 and 558 nm attributed to π* → σ*(Rh-O) and π* → σ* transitions, respectively 44,45.…”

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confidence: 99%

Heterometallic one-dimensional chain with tetradeca metal repetition constructed by amidate bridged dirhodium and pivalate bridged diplatinum complexes influenced by hydrogen bonding

2016

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A novel heterometallic one-dimensional (1-D) chain complex, [{Rh2(acam)4}3{Pt2(OPiv)2(NH3)4}4](ClO4)8 (4, acam = acetamidate, OPiv = pivalate), has been synthesized and characterized by single-crystal X-ray analysis and diffuse reflectance spectroscopy. Complex 4 comprises [Rh2(acam)4] (i.e. [Rh2]) and [Pt2(OPiv)2(NH3)4](ClO4)2 (i.e. [Pt2]), where Rh and Pt atoms are axially linked by metal-metal bonds with a repetition of -{[Rh2]-[Pt2]-[Rh2]-[Pt2]-[Rh2]-[Pt2]-[Pt2]}n-. All metal oxidation states in 4, determined by structural and X-ray photoelectron spectral analyses, are +2. The unbridged Rh-Pt and Pt-Pt bonds in 4 are supported by multiple hydrogen bonds; the distances of Rh-Pt bonds are relatively longer than those in previously reported 1-D chains despite smaller torsion angles between the Rh and Pt coordination planes. Diffuse reflectance spectra revealed that the electronic structure of 4 has a larger gap between filled and vacant σ-type orbitals and a smaller gap between a filled π*(Rh2) and a vacant σ-type orbital.

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Electrochemical characterization of a novel rhodium(II) dimer, Rh2(ONHCCF3)4

Cited by 27 publications

References 3 publications

Synthesis, characterisation and crystal structure of a dirhodium(II) compound with two bridging trifluoroacetamidate ligands

Synthesis, characterisation and crystal structure of a dirhodium(II) compound with two bridging trifluoroacetamidate ligands

Synthesis, Electrochemistry, and Spectroscopic Characterization of Bis-dirhodium Complexes Linked by Axial Ligands

Heterometallic one-dimensional chain with tetradeca metal repetition constructed by amidate bridged dirhodium and pivalate bridged diplatinum complexes influenced by hydrogen bonding

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