Unexpected reactions of NHC*-Cu
| Autor: | Hessah T. Althani, Daniel Marhöfer, Matthias Tacke, Helge Müller-Bunz |
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| Rok vydání: | 2019 |
| Předmět: |
crystal structure
Thio Thiocyanate 010402 general chemistry 01 natural sciences Medicinal chemistry Research Communications chemistry.chemical_compound selenocyanate N-Heterocyclic carbene Moiety General Materials Science thiocyanate silver(I) Substitution reaction d10 electron configuration thiocyanate Crystallography Thiocyanate 010405 organic chemistry Crystal structure selenocyanate General Chemistry Condensed Matter Physics Cyanate 0104 chemical sciences copper(I) Solvent chemistry QD901-999 Selenocyanate Diethyl ether Copper(I) Carbene |
| Zdroj: | Acta Crystallographica Section E: Crystallographic Communications Acta Crystallographica Section E: Crystallographic Communications, Vol 75, Iss 11, Pp 1657-1663 (2019) |
| ISSN: | 2056-9890 |
| Popis: | This article reports the unexpected reactions of Cu and Ag NHC bromides with potassium thio- or selenocyanates. It contains the first report of the boomerang-shaped [Ag(SCN)3]2− ion. The reactions of N-heterocyclic carbene CuI and AgI halides with potassium thio- or selenocyanate gave unexpected products. The attempted substitution reaction of bromido(1,3-dibenzyl-4,5-diphenylimidazol-2-ylidene)silver (NHC*—Ag—Br) with KSCN yielded bis[bis(1,3-dibenzyl-4,5-diphenylimidazol-2-ylidene)silver(I)] tris(thiocyanato)argentate(I) diethyl ether disolvate, [Ag(C29H24N2)2][Ag(NCS)3]·2C4H10O or [NHC*2Ag]2[Ag(SCN)3]·2Et2O, (1), while reaction with KSeCN led to bis(μ-1,3-dibenzyl-4,5-diphenyl-2-selenoimidazole-κ2 Se:Se)bis[bromido(1,3-dibenzyl-4,5-diphenyl-2-selenoimidazole-κSe)silver(I)] dichloromethane hexasolvate, [Ag2Br2(C29H24N2Se)4]·6CH2Cl2 or (NHC*Se)4Ag2Br2·6CH2Cl2, (2), via oxidation of the NHC* fragment to 2-selenoimidazole. This oxidation was observed again in the reaction of NHC*—Cu—Br with KSeCN, yielding catena-poly[[[(1,3-dibenzyl-4,5-diphenyl-2-selenoimidazole-κSe)copper(I)]-μ-cyanido-κ2 C:N] acetonitrile monosolvate], {[Cu(CN)(C29H24N2Se)]·C2H3N}n or NHC*Se—CuCN·CH3CN, (3). Compound (1) represents an organic/inorganic salt with AgI in a linear coordination in each of the two cations and in a trigonal coordination in the anion, accompanied by diethyl ether solvent molecules. The tri-blade boomerang-shaped complex anion [Ag(SCN)3]2− present in (1) is characterized by X-ray diffraction for the first time. Compound (2) comprises an isolated centrosymmetric molecule with AgI in a distorted tetrahedral BrSe3 coordination, together with dichloromethane solvent molecules. Compound (3) exhibits a linear polymeric 1 ∞[Cu—C≡N—Cu—] chain structure with a selenoimidazole moiety additionally coordinating to each CuI atom, and completed by acetonitrile solvent molecules. Electron densities associated with an additional ether solvent molecule in (1) and two additional dichloromethane solvent molecules in (2) were removed with the SQUEEZE procedure [Spek (2015 ▸). Acta Cryst. C71, 9–18] in PLATON. |
| Databáze: | OpenAIRE |
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