Linear and Bent Nitric Oxide Ligand Binding in an Asymmetric Butterfly Complex
| Autor: | Manuel Quiroz, Marcetta Y. Darensbourg, Joseph H. Reibenspies, Paulina Guerrero-Almaraz |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Synthon Bent molecular geometry chemistry.chemical_element 010402 general chemistry 01 natural sciences Quadruple bond 0104 chemical sciences Dication Inorganic Chemistry Crystallography chemistry.chemical_compound chemistry Unpaired electron Molybdenum Molecular orbital Physical and Theoretical Chemistry Acetonitrile |
| Zdroj: | Inorganic chemistry. 60(21) |
| ISSN: | 1520-510X |
| Popis: | Two synthetic approaches to install metallodithiolate ligands on molybdenum centers using the synthons [Mo2(CH3CN)10]4+ and (N2S2)Co(NO) [N2S2 = N,N-bis(2-mercaptoethyl)-1,4-diazacycloheptane and NO = nitric oxide], or [Mo(NO)2(CH3CN)4]2+ (CH3CN = acetonitrile) and [(N2S2)Co]2 lead to a bis-nitrosylated, trimetallic dication, CoMoCo'. This unique asymmetric butterfly complex, with S = 1, has a bent NO within the small {Co(NO)}8 wing (denoted as Co), reflecting CoIII(NO-), and is S-bridged to a linear {Mo(NO)}6 diamagnetic unit. The latter is further S-bridged to a pentacoordinate (N2S2)CoIII(CH3CN) donor in the larger wing and is the origin of the two unpaired electrons, denoted as Co'. The asymmetry in Mo-Co distances, 3.33 A in the Co wing and 2.73 A in the Co' wing, indicated a Mo-Co' bonding interaction. The transfer of NO from (N2S2)Co(NO) in the former path is needed to cleave the strong quadruple bond in [Mo≣Mo]4+, with the energetic cost compensated for via a one-electron bond between Mo and Co', as indicated by natural bonding orbital analysis. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|