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Versatile Coordination of Ag^I and Cu^I Ions towards cyclo-As₅ Ligands.

ABSTRACT: The reactions of the cyclo-As₅ complex [Cp*Fe(η⁵ -As₅ )] (B) with the Ag^I and Cu^I salts of the weakly coordinating anion (WCA) [FAl{OC₆ F₁₀ (C₆ F₅ )}₃ ]^- ([FAl]^- ) are studied. These reactions allow the synthesis of the mononuclear complexes [M(η⁵ : η² -B)₂ ][FAl] (M=Ag (1), Cu (2)) when a ratio of B/M(FAl) 2 : 1 is used. Compound 1 shows an unusual disorder of the central Ag^I cation between two π-coordinating cyclo-As₅ ligands, which is absent in 2 pointing to a weak interaction of the Ag center towards the cyclo-As₅ ligands in B. When the ratio of B/Ag(FAl) is changed to 3 : 1 or 1 : 1, the respective coordination compounds [Ag(η² -B)₃ ][FAl] (3) and [Ag₂ (η² : η² -B)₂ ][FAl]₂ (4) are accessible. The coordination modes of the cyclo-As₅ units in 1, 3 and 4 are all different, reflecting the adaptive coordination behavior of B towards Ag^I ions. The optimized geometries in the gas phase of 1-4 are determined by DFT calculations to support the bonding situation observed in their solid-state structures.

SUBMITTER: Moussa ME

PROVIDER: S-EPMC8361777 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Copper-dependent metalloenzymes are widespread throughout metabolic pathways, coupling the reduction of O2 with the oxidation of organic substrates. Small-molecule synthetic analogs are useful platforms to generate L/Cu/O2 species that reproduce the structural, spectroscopic, and reactive properties of some copper-/O2-dependent enzymes. Landmark studies have shown that the conversion between dicopper(II)-peroxo species (L2CuII2(O22-) either side-on peroxo, SP, or end-on trans-peroxo, TP) and dicopper(III)-bis(μ-oxo) (L2CuIII2(O2-)2: O) can be controlled through ligand design, reaction conditions (temperature, solvent, and counteranion), or substrate coordination. We recently published ( J. Am. Chem. Soc. 2012 , 134 , 8513 , DOI: 10.1021/ja300674m ) the crystal structure of an unusual SP species [(MeAN)2CuII2(O22-)]2+ (SPMeAN, MeAN: N-methyl-N,N-bis[3-(dimethylamino)propyl]amine) that featured an elongated O-O bond but did not lead to O-O cleavage or reactivity toward external substrates. Herein, we report that SPMeAN can be activated to generate OMeAN and perform the oxidation of external substrates by two complementary strategies: (i) coordination of substituted sodium phenolates to form the substrate-bound OMeAN-RPhO- species that leads to ortho-hydroxylation in a tyrosinase-like fashion and (ii) addition of stoichiometric amounts (1 or 2 equiv) of Lewis acids (LA's) to form an unprecedented series of O-type species (OMeAN-LA) able to oxidize C-H and O-H bonds. Spectroscopic, computational, and mechanistic studies emphasize the unique plasticity of the SPMeAN core, which combines the assembly of exogenous reagents in the primary (phenolates) and secondary (Lewis acids association to the MeAN ligand) coordination spheres with O-O cleavage. These findings are reminiscent of the strategy followed by several metalloproteins and highlight the possible implication of O-type species in copper-/dioxygen-dependent enzymes such as tyrosinase (Ty) and particulate methane monooxygenase (pMMO).

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Versatile Coordination of AgI and CuI Ions towards cyclo-As5 Ligands.

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Versatile Coordination of Ag^I and Cu^I Ions towards cyclo-As₅ Ligands.