%0 Journal Article %1 Albrecht.2000b %A Albrecht, Markus %A Huebler, Klaus %A Zalis, Stanislav %A Kaim, Wolfgang. %D 2000 %J Inorganic Chemistry %K benzimidazole complex complex;electrochem copper electrochem;copper electrochem;crystal methylthiomethyl methylthiomethylbenzimidazole prepn redox structure %N 21 %P 4731--4734 %R 10.1021/ic000021u %T Crucial Role of Cu-S Bonding for Structural Changes Accompanying the Reversible CuI/CuII Transition in an Unrestrained Cu(N$\cap$S)2 Coordination Arrangement. An Experimental and DFT Study %V 39 %X The structure of reversibly oxidizable Cu(mmb)2(BF4) with 1-methyl-2-(methylthiomethyl)-1H-benzimidazole (mmb) as bidentate N,S-donor ligand was detd. and compared with that of the copper(II) species Cu(mmb)2(h1-ClO4)(ClO4). In the complex ions of the equil. CuI(mmb)2+ + ClO4- .dblharw. e- + CuII(mmb)2(h1-ClO4)+ the almost linear N-Cu-N backbone is invariant whereas the bonds to the thioether sulfur centers and esp. the changing S-Cu-S angle (145.18(5)° for the CuII species, 109.33(3)° for the CuI form) reflect the metal oxidn. state. In contrast to the perchlorate coordinating copper(II) species, CuI(mmb)2(BF4) contains a cation with a very large vacant site at the metal center, resulting in elliptical channels within the crystal. DFT calcns. on CuI(mb)2+, CuII(mb)22+, and CuII(mb)2(OClO3)+ with mb = 2-methylthiomethyl-1H-benzimidazole confirm the essential role of the metal-sulfur bonds in responding to the reversible CuI/II electron transfer process, even in the absence of electronically stronger interacting thiolate sulfur centers or sophisticated oligodentate ligands. on SciFinder(R)

@article{Albrecht.2000b, abstract = {The structure of reversibly oxidizable [Cu(mmb)2](BF4) with 1-methyl-2-(methylthiomethyl)-1H-benzimidazole (mmb) as bidentate N,S-donor ligand was detd. and compared with that of the copper(II) species [Cu(mmb)2(\textgreek{h}1-ClO4)](ClO4). In the complex ions of the equil. [CuI(mmb)2]+ + ClO4- .dblharw. e- + [CuII(mmb)2(\textgreek{h}1-ClO4)]+ the almost linear N-Cu-N backbone is invariant whereas the bonds to the thioether sulfur centers and esp. the changing S-Cu-S angle (145.18(5)° for the CuII species, 109.33(3)° for the CuI form) reflect the metal oxidn. state. In contrast to the perchlorate coordinating copper(II) species, [CuI(mmb)2](BF4) contains a cation with a very large vacant site at the metal center, resulting in elliptical channels within the crystal. DFT calcns. on [CuI(mb)2]+, [CuII(mb)2]2+, and [CuII(mb)2(OClO3)]+ with mb = 2-methylthiomethyl-1H-benzimidazole confirm the essential role of the metal-sulfur bonds in responding to the reversible CuI/II electron transfer process, even in the absence of electronically stronger interacting thiolate sulfur centers or sophisticated oligodentate ligands. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Albrecht, Markus and Huebler, Klaus and Zalis, Stanislav and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/292d741a8a4ca41e04341e4a9c6f4c6e8/huebleriac}, doi = {10.1021/ic000021u}, interhash = {eb9e151b985b5eb0fd147f1b8f733241}, intrahash = {92d741a8a4ca41e04341e4a9c6f4c6e8}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {benzimidazole complex complex;electrochem copper electrochem;copper electrochem;crystal methylthiomethyl methylthiomethylbenzimidazole prepn redox structure}, number = 21, pages = {4731--4734}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Crucial Role of Cu-S Bonding for Structural Changes Accompanying the Reversible CuI/CuII Transition in an Unrestrained Cu(N$\cap$S)2 Coordination Arrangement. An Experimental and DFT Study}, volume = 39, year = 2000 }