Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole

Ganguly, Šumit; Renz, Diemo; Giles, Logan J.; Gagnon, Kevin J.; McCormick, Laura J.; Conradie, Jeanet; Sarangi, Ritimukta; Ghosh, Abhik

doi:10.1021/acs.inorgchem.7b01828

Cited by 52 publications

(54 citation statements)

References 86 publications

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“…Recently, Nocera and Kar independently reported that several copper complexes of meso ‐aryl‐substituted corroles consist of the central copper(II) ion and the divalent corrole π‐radical ligand with strong antiferromagnetic interaction between the copper(II) and the π‐radical fragment, thereby behaving as an overall singlet spin‐state even at room temperature. Similar ligand non‐innocent behaviors have also been known for silver octabromocorroles, chloroiron and nitrosoiron corroles, triphenylphosphine cobalt corroles, and chloromanganese corroles . Another important observation is the metal‐ligand interaction depending on the size of the ligand.…”

Section: Introductionsupporting

confidence: 58%

Bis‐copper(II) Complex of Triply‐linked Corrole Dimer and Its Dication

Ooi

Tanaka

Ikeue

et al. 2018

Chemistry An Asian Journal

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Copper complexeso fc orroles have recently been as ubjecto fk een interest duet ot heir ligand non-innocent character and uniquer edox properties. Here we investigated bis-copper complex of at riply-linked corrole dimer that serves as apairofd ivalent metal ligands but can be reduced to ap air of trivalent metal ligands. Reaction of triply-linked corrole dimer 2 with Cu(acac) 2 (acac = acetylacetonate) gave bis-copper(II)c omplex 2Cu as ah ighly planar molecule with am ean-plane deviation value of 0.020 ,w here the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF 4 gave complex 3Cu,w hich was characterizeda sabiscopper(II) complex of ad icationic triply-linked corrole dimer not as the corresponding bis-copper(III) complex. In accord with this assignment, the structuralp arameters aroundt he copperi ons were revealed to be quite similarf or 2Cu and 3Cu.I mportantly,t he magnetic spin-spin interactiond iffers depending on the redox-state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu.[a] S.

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Section: Introductionsupporting

confidence: 58%

Bis‐copper(II) Complex of Triply‐linked Corrole Dimer and Its Dication

Ooi

Tanaka

Ikeue

et al. 2018

Chemistry An Asian Journal

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“…[11] Previous studies have shown that this level accurately reproduces geometries and energies of cobalt corrole complexes. [1c], …”

Section: Methodsmentioning

confidence: 99%

Cobalt Corroles with Bis‐Ammonia or Mono‐DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties

et al. 2018

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Four bis-ammonia ligated cobalt corroles and four mono-DMSO ligated cobalt corroles with different meso-aryl substituents on the macrocycle (A 2 B-and A 3 -corroles) were synthesized and investigated as to their electrochemical and spectroscopic properties under different solution conditions. The complexation energies of the investigated cobalt corroles were [a] Scheme 2. Structures of the investigated bis-ammonia and mono-DMSO meso-aryl cobalt corroles. dinated form of A 3 -and/or A 2 B-cobalt corroles) which will bind CO. Very recently, concentrations of CO as low as a few hundred ppb were measured by SAW sensors emphasizing the interest of such sensors for the detection of carbon monoxide. [4] Scheme 3. Synthesis of mono-DMSO and bis-NH 3 cobalt corroles.The eight cobalt corroles 1DMSO-4DMSO and 1NH 3 -4NH 3 were prepared according to the synthetic procedure shown in Scheme 3. The A 3 -and A 2 B-free-base corroles 1H-4H were synthesized according to published procedures described by Gryko and co-workers, [5] and metallated with Co(OAc) 2 in DMSO to give the cobalt complexes 1DMSO-4DMSO, each with a single DMSO molecule as axial ligand. These mono-DMSO adducts were then treated with an aqueous ammonia solution to give the bis-ammonia derivatives 1NH 3 -4NH 3 in 79-94 % yield. Spectroscopic Characterization1DMSO-4DMSO were measured at a concentration of 10 -3 M in both CH 2 Cl 2 and DMSO containing 0.1 M TBAP (Figure 2). In CH 2 Cl 2 the spectra are characterized by a Soret band at 379-387 nm and a single less intense band at 562-566 nm. There is also a shoulder on the Soret band at about 414-417 nm. These spectra are similar to previously reported UV/Vis spectra for a related series of mono-DMSO ligated cobalt nitrophenylcorroles under the same solution conditions. [3] Similar spectral patterns are seen for 2DMSO, 3DMSO and 4DMSO in the two solvents but this is not the case for 1DMSO as seen in Figure 2. The spectrum in CH 2 Cl 2 (Figure 2a) is assigned to the mono-DMSO adduct while in DMSO a mixture of the five-and six-coordinate derivatives are proposed to exist, the hexa-coordinate DMSO adduct having bands at 417, 442, 453 and 618 nm as described on the following pages. It should be noted that 1DMSO is the only cobalt corrole among the currently investigated compounds which possesses six electronwithdrawing substituents on the meso-phenyl rings, and this seems to facilitate the binding of a second DMSO molecule to the cobalt center of the neutral compound. Stronger pyridine binding constants were also earlier reported for cobalt corroles with electron-withdrawing substituents on the meso-phenyl rings. [3] UV/Visible spectra of the bis-ammonia complexes 1NH 3 -4NH 3 were also measured at a concentration of 1 × 10 -3 M un-Eur.(CO 2 MePh)Mes 2 CorCo(DMSO) (2DMSO): 88 % yield (211 mg). UV/ Visible (toluene, 1 % DMSO): λ max (ε × 10 -3 L·mol -1 cm -1 ) 383 (62.9), 563 (13.1) nm. 1 H NMR [500 MHz, CDCl 3 + NH 3 (g)]: δ = 8.98 (d,

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“…In recent years, metallocorroles have provided many examples of well-characterized noninnocent systems. [19][20][21][22] Key examples include MnCl, 23 FeCl, [9][10][11][12][13][14][15] FeNO, [24][25][26][27] Fe 2 (μ-O), 28 Copy 29 /DMSO 30 ( py = pyridine), Co-PPh 3 , 31 and Cu [32][33][34][35][36][37][38][39][40] corrole derivatives. It is worth noting that all these involve first-row transition metals.…”

Section: Introductionmentioning

confidence: 99%