Syntheses, structures and bonding of 3d metal alkynyl complexes of cyclam and its derivatives
| Autor: | Susannah D. Banziger, Tong Ren |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Organic Chemistry Chromophore 010402 general chemistry 01 natural sciences Biochemistry Acceptor Medicinal chemistry 0104 chemical sciences Inorganic Chemistry Metal chemistry.chemical_compound Electron transfer chemistry Alkynylation visual_art Cyclam Materials Chemistry Dehydrohalogenation visual_art.visual_art_medium Physical and Theoretical Chemistry Weak base |
| Zdroj: | Journal of Organometallic Chemistry. 885:39-48 |
| ISSN: | 0022-328X |
| Popis: | Described in this review is the chemistry of 3d metal alkynyls based on tetraaza macrocyclic ligands. Both the abundance of 3d metals and easy access to the tetraazacyclotetradecane type ligands make these compounds more affordable and sustainable alternatives to metal alkynyls based on precious metals. Taking advantage of a rich variety of starting materials available in literature, the trans-[M(cyclam)(C2R)2]X type (cyclam = 1,4,8,11-tetraazacyclotetradecane) compounds have been prepared from the reactions between [M(cyclam)X2]X (M = Cr, Fe and Co; X = Cl or OTf) and LiC2R. With [Co(cyclam)Cl2]+, both the {trans-[Co(cyclam)Cl]2(μ-(C≡C)n)}2+ and trans-[Co(cyclam)(C2R)Cl]+ type compounds can be prepared through a dehydrohalogenation reaction. The latter type compounds can undergo a second alkynylation reaction with LiC2R' to afford the dissymmetric trans-[Co(cyclam)(C2R)(C2R')]+ type compounds, including the trans-[Co(cyclam)(C2A)(C2D)]+ dyads with A and D as acceptor and donor chromophores respectively. These compounds are being studied to probe photo-induced electron transfer and related photophysical/photochemical processes. The trans-[Co(cyclam)(C2R)(NCMe)]2+ type complexes react with unactivated HC2R' in the presence of a weak base to provide trans-[Co(cyclam)(C2R)(C2R')]+ in high yields. Similar alkynylation chemistry with complexes of cyclam derivatives, like TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), HMC (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) and DMC (5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane), has been demonstrated with the studies of [Ni(TMC)(C2R)]+, trans-/cis-[Cr(HMC/DMC)(C2R)2]+ and trans-[Co(DMC)(C2R)2]+. |
| Databáze: | OpenAIRE |
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