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Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp₂ TiCl₂ for Catalysis Unveiled.

ABSTRACT: The combination of synthesis, rotating ring-disk electrode (RRDE) and cyclic voltammetry (CV) measurements, and computational investigations with the aid of DFT methods shows how a thiourea, a squaramide, and a bissulfonamide as additives affect the E_q C_r equilibrium of Cp₂ TiCl₂ . We have, for the first time, provided quantitative data for the E_q C_r equilibrium and have determined the stoichiometry of adduct formation of [Cp₂ Ti(III)Cl₂ ]^- , [Cp₂ Ti(III)Cl] and [Cp₂ Ti(IV)Cl₂ ] and the additives. By studying the structures of the complexes formed by DFT methods, we have established the Gibbs energies and enthalpies of complex formation as well as the adduct structures. The results not only demonstrate the correctness of our use of the E_q C_r equilibrium as predictor for sustainable catalysis. They are also a design platform for the development of novel additives in particular for enantioselective catalysis.

SUBMITTER: Hilche T

PROVIDER: S-EPMC7986168 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature

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Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp2 TiCl2 for Catalysis Unveiled.

Hilche Tobias T Reinsberg Philip H PH Klare Sven S Liedtke Theresa T Schäfer Luise L Gansäuer Andreas A

Chemistry (Weinheim an der Bergstrasse, Germany) 20210112 15

The combination of synthesis, rotating ring-disk electrode (RRDE) and cyclic voltammetry (CV) measurements, and computational investigations with the aid of DFT methods shows how a thiourea, a squaramide, and a bissulfonamide as additives affect the Eq Cr equilibrium of Cp2 TiCl2 . We have, for the first time, provided quantitative data for the Eq Cr equilibrium and have determined the stoichiometry of adduct formation of [Cp ...[more]

PMID: 33085978

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Project description:Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.

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Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp₂ TiCl₂ for Catalysis Unveiled.

Publications

Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp<sub>2</sub> TiCl<sub>2</sub> for Catalysis Unveiled.

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