Coordination Complexes of Fullerene C60 with Rhodium {Cp*RhII(μ-Cl)}2(η2,η2-C60) and (Bu4N+){Cp*RhICl(η2-C60)}−. Temperature-Induced Charge Transfer from RhI to η2-C60

Konarev, Dmitri V.; Kuzmin, Alexey V.; Khasanov, Salavat S.; Troyanov, Sergey I.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N.

doi:10.1021/acs.organomet.7b00660

Cited by 6 publications

(1 citation statement)

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“…Such complexes exhibit interesting chemical properties and demonstrate potential use in catalysis and bond activation due to their open shell d 7 character. Even more rare are dirhodium(II,II) complexes that lack a metal–metal bond, the first of which was described in 2015 . These complexes contain bridging halides along with bulky capping ligands for sufficient separation of the two Rh centers.…”

Section: Introductionmentioning

confidence: 99%

Three Reversible Redox States of Thiolate-Bridged Dirhodium Complexes without Metal–Metal Bonds

Coll

Dunbar

2020

J. Am. Chem. Soc.

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An unusual dinuclear rhodium complex with the anionic 2-mercapto-6-methylpyridinate (mmp) bridging ligand is reported which is capable of undergoing significant variations in its structural and coordination environments as a result of two reversible redox events at accessible potentials (E 1/2 = 0.014, 0.52 V vs Ag/AgCl). The large degree of separation between these redox states (ΔE = 0.51 V, K C = 4.17 × 108) allows for the chemical isolation of three distinct complexes 1, 2, and 3, in which the oxidation states of each Rh center are Rh2 I,I, Rh2 I,II, and Rh2 II,II, respectively, and whose solid-state structures were elucidated by single crystal X-ray diffraction studies. Complex 2 is an unprecedented type of mixed valence dirhodium species whose electron paramagnetic resonance spectrum revealed a delocalization of the unpaired electron through the thiolate-bridging ligand. Intervalence charge transfer occurs between the Rh centers, as evidenced by a broad absorption in the near-infrared region (λmax = 1187 nm). The structure of 3 is quite rare in that it lacks the typical RhII–RhII σ bond, but significant orbital overlap between the Rh 4d z 2 and S 3p z orbitals results in a strong antiferromagnetic coupling (computed J = −1516.9 cm–1). Complex 3 also absorbs low-energy light (λmax = 779 nm). Spectroscopic and magnetic measurements are supported by density functional theory methods, which further elucidate the nature of the ground state energies, frontier orbital characters, excited state transitions, and presence of weak Rh–Rh natural bond orbital interactions.

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Section: Introductionmentioning

confidence: 99%

Three Reversible Redox States of Thiolate-Bridged Dirhodium Complexes without Metal–Metal Bonds

Coll

Dunbar

2020

J. Am. Chem. Soc.

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Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl‐Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers

Konarev

Kuzmin

Khasanov

et al. 2018

Chemistry A European J

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Reduction methods for the preparation of coordination complexes of titanium(IV) and indium(III) phthalocyanines (Pc) with organic dyes such as indigo, thioindigo, and squarylium dye III (SQ) have been developed, which allow one to obtain crystalline {cryptand(K )}{(cis-indigo-O,O) Ti (Pc )}(Cl )⋅C H Cl (1), {cryptand(K )}{(cis-thioindigo-O,O) In (Pc )} ⋅C H Cl (2), and {cryptand(K )}{[(SQ) -O,O] In (Pc )} ⋅3.5 C H Cl (3) complexes. The formation of these complexes is accompanied by the reduction of the starting dyes to the anionic state. Transition of trans-indigo or trans-thioindigo to the cis conformation in 1 and 2 provides coordination of both carbonyl oxygen atoms of the dye to Ti Pc or In Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ ) dimers in 3. These dimers have two closely positioned carbonyl oxygen atoms coordinated to In Pc. Dianionic Pc macrocycles have been found in 1-3. The complexes contain two chromophore molecules at one metal center. However, their optical spectra are defined mainly by absorption bands of the metal phthalocyanines.

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Radical anion and coordination compounds of polyconjugated molecules:potential organic materials with unusual magnetic, conducting and optical properties

Konarev

2020

Mendeleev Communications

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Coordination Complexes of Fullerene C₆₀ with Rhodium {CpRh^II(μ-Cl)}₂(η²,η²-C₆₀) and (Bu₄N⁺){CpRh^ICl(η²-C₆₀)}⁻. Temperature-Induced Charge Transfer from Rh^I to η²-C₆₀

Cited by 6 publications

References 39 publications

Three Reversible Redox States of Thiolate-Bridged Dirhodium Complexes without Metal–Metal Bonds

Three Reversible Redox States of Thiolate-Bridged Dirhodium Complexes without Metal–Metal Bonds

Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl‐Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers

Radical anion and coordination compounds of polyconjugated molecules:potential organic materials with unusual magnetic, conducting and optical properties

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