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Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals.

ABSTRACT: We report on the structures of three unprecedented heteroleptic Sb-centered radicals [L(Cl)Ga](R)Sb. (2-R, R=B[N(Dip)CH]2 2-B, 2,6-Mes2 C6 H3 2-C, N(SiMe3 )Dip 2-N) stabilized by one electropositive metal fragment [L(Cl)Ga] (L=HC[C(Me)N(Dip)]2 , Dip=2,6-i-Pr2 C6 H3 ) and one bulky B- (2-B), C- (2-C), or N-based (2-N) substituent. Compounds 2-R are predominantly metal-centered radicals. Their electronic properties are largely influenced by the electronic nature of the ligands R, and significant delocalization of unpaired-spin density onto the ligands was observed in 2-B and 2-N. Cyclic voltammetry (CV) studies showed that 2-B undergoes a quasi-reversible one-electron reduction, which was confirmed by the synthesis of [K([2.2.2]crypt)][L(Cl)GaSbB[N(Dip)CH]2 ] ([K([2.2.2]crypt)][2-B]) containing the stibanyl anion [2-B]- , which was shown to possess significant Sb-B multiple-bonding character.

SUBMITTER: Helling C

PROVIDER: S-EPMC7216903 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals.

Helling Christoph C Cutsail George E GE Weinert Hanns H Wölper Christoph C Schulz Stephan S

Angewandte Chemie (International ed. in English) 20200310 19

We report on the structures of three unprecedented heteroleptic Sb-centered radicals [L(Cl)Ga](R)Sb. (2-R, R=B[N(Dip)CH]2 2-B, 2,6-Mes2 C6 H3 2-C, N(SiMe3 )Dip 2-N) stabilized by one electropositive metal fragment [L(Cl)Ga] (L=HC[C(Me)N(Dip)]2 , Dip=2,6-i-Pr2 C6 H3 ) and one bulky B- (2-B), C- (2-C), or N-based (2-N) substituent. Compounds 2-R are predominantly metal-centered radicals. T ...[more]

PMID: 32048388

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Project description:The nature of the ligand is an important aspect of controlling the structure and reactivity in coordination chemistry. In connection with our study of heme-copper-oxygen reactivity relevant to cytochrome c oxidase dioxygen-reduction chemistry, we compare the molecular and electronic structures of two high-spin heme-peroxo-copper [Fe(III)O(2)(2-)Cu(II)](+) complexes containing N(4) tetradentate (1) or N(3) tridentate (2) copper ligands. Combining previously reported and new resonance Raman and EXAFS data coupled to density functional theory calculations, we report a geometric structure and more complete electronic description of the high-spin heme-peroxo-copper complexes 1 and 2, which establish mu-(O(2)(2-)) side-on to the Fe(III) and end-on to Cu(II) (mu-eta(2):eta(1)) binding for the complex 1 but side-on/side-on (mu-eta(2):eta(2)) mu-peroxo coordination for the complex 2. We also compare and summarize the differences and similarities of these two complexes in their reactivity toward CO, PPh(3), acid, and phenols. The comparison of a new X-ray structure of mu-oxo complex 2a with the previously reported 1a X-ray structure, two thermal decomposition products respectively of 2 and 1, reveals a considerable difference in the Fe-O-Cu angle between the two mu-oxo complexes ( angleFe-O-Cu = 178.2 degrees in 1a and angleFe-O-Cu = 149.5 degrees in 2a). The reaction of 2 with 1 equiv of an exogenous nitrogen-donor axial base leads to the formation of a distinctive low-temperature-stable, low-spin heme-dioxygen-copper complex (2b), but under the same conditions, the addition of an axial base to 1 leads to the dissociation of the heme-peroxo-copper assembly and the release of O(2). 2b reacts with phenols performing H-atom (e(-) + H(+)) abstraction resulting in O-O bond cleavage and the formation of high-valent ferryl [Fe(IV)=O] complex (2c). The nature of 2c was confirmed by a comparison of its spectroscopic features and reactivity with those of an independently prepared ferryl complex. The phenoxyl radical generated by the H-atom abstraction was either (1) directly detected by electron paramagnetic resonance spectroscopy using phenols that produce stable radicals or (2) indirectly detected by the coupling product of two phenoxyl radicals.

Dataset Information

Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals.

Publications

Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals.

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