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Unusual cyanide and methyl binding modes at a dicobalt macrocycle following acetonitrile C-C bond activation.

ABSTRACT: This communication describes the C-C bond activation of acetonitrile and the trapping of the methyl and cyanide fragments by macrocyclic, dicobalt complexes. Both products display unique structural features as a result of the constraints imposed by the macrocycle. The bridged species [(³PDI₂)Co₂(μ-CN)(PMe₃)₂][OTf] ([Co₂CN]⁺) exhibits atypical Co-CN-Co binding, and upon either phosphine dissociation or oxidation, the flexible ligand framework is able to switch between different binding modes of μ-cyanide. Further, the bridging methyl species [(³PDI₂)Co₂(μ-CH₃)(PMe₃)][OTf] ([Co₂CH₃]⁺) is the first structurally characterized dicobalt complex with a bridging methyl group.

SUBMITTER: Spentzos AZ

PROVIDER: S-EPMC7442599 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Unusual cyanide and methyl binding modes at a dicobalt macrocycle following acetonitrile C-C bond activation.

Spentzos Ariana Z AZ Gau Michael R MR Carroll Patrick J PJ Tomson Neil C NC

Chemical communications (Cambridge, England) 20200722 67

This communication describes the C-C bond activation of acetonitrile and the trapping of the methyl and cyanide fragments by macrocyclic, dicobalt complexes. Both products display unique structural features as a result of the constraints imposed by the macrocycle. The bridged species [(3PDI2)Co2(μ-CN)(PMe3)2][OTf] ([Co2CN]+) exhibits atypical Co-CN-Co binding, and upon either phosphine dissociation or oxidation, the fle ...[more]

PMID: 32696777

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Project description:The complex of cobalt(II) with the ligand 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]heptadeca-1(17)2,11,13,15-pentaene (CoN4[11.3.1]) has been shown to bind two molecules of cyanide in a cooperative fashion with an association constant of 2.7 (±0.2) × 10(5). In vivo, irrespective of whether it is initially administered as the Co(II) or Co(III) cation, EPR spectroscopic measurements on blood samples show that at physiological levels of reductant (principally ascorbate) CoN4[11.3.1] becomes quantitatively reduced to the Co(II) form. However, following addition of sodium cyanide, a dicyano Co(III) species is formed, both in blood and in buffered aqueous solution at neutral pH. In keeping with other cobalt-containing cyanide-scavenging macrocycles like cobinamide and cobalt(III) meso-tetra(4-N-methylpyridyl)porphine, we found that CoN4[11.3.1] exhibits rapid oxygen turnover in the presence of the physiological reductant ascorbate. This behavior could potentially render CoN4[11.3.1] cytotoxic and/or interfere with evaluations of the antidotal capability of the complex toward cyanide through respirometric measurements, particularly since cyanide rapidly inhibits this process, adding further complexity. A sublethal mouse model was used to assess the effectiveness of CoN4[11.3.1] as a potential cyanide antidote. The administration of CoN4[11.3.1] prophylactically to sodium cyanide-intoxicated mice resulted in the time required for the surviving animals to recover from "knockdown" (unconsciousness) being significantly decreased (3 ± 2 min) compared to that of the controls (22 ± 5 min). All observations are consistent with the demonstrated antidotal activity of CoN4[11.3.1] operating through a cyanide-scavenging mechanism, which is associated with a Co(II) → Co(III) oxidation of the cation. To test for postintoxication neuromuscular sequelae, the ability of mice to remain in position on a rotating cylinder (RotaRod test) was assessed during and after recovery. While intoxicated animals given CoN4[11.3.1] did recover ∼30 min more quickly than controls given only toxicant, there were no indications of longer-term problems in either group, as determined by continuing the RotaRod testing up to 24 h after the intoxications and routine behavioral observations for a further week.

Dataset Information

Unusual cyanide and methyl binding modes at a dicobalt macrocycle following acetonitrile C-C bond activation.

Publications

Unusual cyanide and methyl binding modes at a dicobalt macrocycle following acetonitrile C-C bond activation.

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