Structurally characterized 2-methylselenomethyl-1H-benzimidazole (msbi) is shown to form complexes in 2:1 ratio with copper(II). Whereas the central cation Cu(msbi)2Cl+ (1+) in Cu(msbi)2ClCl·2MeOH crystallizes in an approx. mixed square-pyramidal/trigonal-bipyramidal structure (t = 0.52) with the second and third row atoms chlorine and selenium in the equatorial plane, the related Cu(msbi)2(MeOH)(BF4)2, 2(BF4)2, exhibits a closer to square-pyramidal arrangement with t = 0.36 for that complex dication 22+. In both cases, the Cu-N bonds are short at about 1.94 \AA, whereas the Cu-Se distances vary between 2.62 \AA for 1+ and ca. 2.54 \AA for 22+. Slight differences between the Jahn-Teller influenced species 1+ and 22+ are also apparent from absorption and EPR spectra. Since copper(I) complexes of msbi suitable for crystal structure anal. could not be obtained, the related 1-methyl-2-phenylselenomethyl-1H-benzimidazole (mpsbi) was prepd. and used to obtain Cu(mpsbi)2(X), 3(X) (X = BF4 or PF6). The copper(I) ion in the corresponding cation 3+ shows a DFT-reproduced distorted tetrahedral configuration with an N-CuI-N angle at 146.7(3)°, less straightened than the ca. 170° in similar CuI complexes with thioether-1H-benzimidazole ligands. A copper(I) compd. Cu(psbi)2Cu(psbi)(psbi-H+)(PF6), 44'(PF6), with another related ligand, 2-phenylselenomethyl-1H-benzimidazole (psbi), was crystd. in partially benzimidazole-deprotonated acetonitrile solvate form, showing short Cu-N bonds of 1.898(5) \AA, an N-CuI-N angle of 157.5(3)°, a Se···Se interaction at 3.6237(3) \AA, and a very small Se-Cu-Se angle of 78.23(4)°. The different responses resulting from thioether and selenoether coordination to copper in the complexes at hand are being discussed. on SciFinder(R)
%0 Journal Article
%1 Leboschka.2009
%A Leboschka, Markus
%A Sieger, Monika
%A Sarkar, Biprajit
%A Heck, Juergen
%A Niemeyer, Mark
%A Bubrin, Denis
%A Lissner, Falk
%A Schleid, Thomas
%A Zalis, Stanislav
%A Su, Cheng-Yong
%A Kaim, Wolfgang.
%D 2009
%J Zeitschrift fuer Anorganische und Allgemeine Chemie
%K alkylselenomethylbenzimidazole alkylselenophenylbenzimidazole alkylselenophenylbenzimidazole;optimized copper methylmethylthiomethylbenzimidazole mol prepn;crystal structure
%N 13-14
%P 2177--2184
%R 10.1002/zaac.200900265
%T 2-Organoselenomethyl-1H-benzimidazole Complexes of Copper(II) and Copper(I)
%V 635
%X Structurally characterized 2-methylselenomethyl-1H-benzimidazole (msbi) is shown to form complexes in 2:1 ratio with copper(II). Whereas the central cation Cu(msbi)2Cl+ (1+) in Cu(msbi)2ClCl·2MeOH crystallizes in an approx. mixed square-pyramidal/trigonal-bipyramidal structure (t = 0.52) with the second and third row atoms chlorine and selenium in the equatorial plane, the related Cu(msbi)2(MeOH)(BF4)2, 2(BF4)2, exhibits a closer to square-pyramidal arrangement with t = 0.36 for that complex dication 22+. In both cases, the Cu-N bonds are short at about 1.94 \AA, whereas the Cu-Se distances vary between 2.62 \AA for 1+ and ca. 2.54 \AA for 22+. Slight differences between the Jahn-Teller influenced species 1+ and 22+ are also apparent from absorption and EPR spectra. Since copper(I) complexes of msbi suitable for crystal structure anal. could not be obtained, the related 1-methyl-2-phenylselenomethyl-1H-benzimidazole (mpsbi) was prepd. and used to obtain Cu(mpsbi)2(X), 3(X) (X = BF4 or PF6). The copper(I) ion in the corresponding cation 3+ shows a DFT-reproduced distorted tetrahedral configuration with an N-CuI-N angle at 146.7(3)°, less straightened than the ca. 170° in similar CuI complexes with thioether-1H-benzimidazole ligands. A copper(I) compd. Cu(psbi)2Cu(psbi)(psbi-H+)(PF6), 44'(PF6), with another related ligand, 2-phenylselenomethyl-1H-benzimidazole (psbi), was crystd. in partially benzimidazole-deprotonated acetonitrile solvate form, showing short Cu-N bonds of 1.898(5) \AA, an N-CuI-N angle of 157.5(3)°, a Se···Se interaction at 3.6237(3) \AA, and a very small Se-Cu-Se angle of 78.23(4)°. The different responses resulting from thioether and selenoether coordination to copper in the complexes at hand are being discussed. on SciFinder(R)
@article{Leboschka.2009,
abstract = {Structurally characterized 2-methylselenomethyl-1H-benzimidazole (msbi) is shown to form complexes in 2:1 ratio with copper(II). Whereas the central cation [Cu(msbi)2Cl]+ (1+) in [Cu(msbi)2Cl]Cl·2MeOH crystallizes in an approx. mixed square-pyramidal/trigonal-bipyramidal structure (\textgreek{t} = 0.52) with the second and third row atoms chlorine and selenium in the equatorial plane, the related [Cu(msbi)2(MeOH)](BF4)2, [2](BF4)2, exhibits a closer to square-pyramidal arrangement with \textgreek{t} = 0.36 for that complex dication 22+. In both cases, the Cu-N bonds are short at about 1.94 {\AA}, whereas the Cu-Se distances vary between 2.62 {\AA} for 1+ and ca. 2.54 {\AA} for 22+. Slight differences between the Jahn-Teller influenced species 1+ and 22+ are also apparent from absorption and EPR spectra. Since copper(I) complexes of msbi suitable for crystal structure anal. could not be obtained, the related 1-methyl-2-phenylselenomethyl-1H-benzimidazole (mpsbi) was prepd. and used to obtain [Cu(mpsbi)2](X), [3](X) (X = BF4 or PF6). The copper(I) ion in the corresponding cation 3+ shows a DFT-reproduced distorted tetrahedral configuration with an N-CuI-N angle at 146.7(3)°, less straightened than the ca. 170° in similar CuI complexes with thioether-1H-benzimidazole ligands. A copper(I) compd. [Cu(psbi)2][Cu(psbi)(psbi-H+)](PF6), [4][4'](PF6), with another related ligand, 2-phenylselenomethyl-1H-benzimidazole (psbi), was crystd. in partially benzimidazole-deprotonated acetonitrile solvate form, showing short Cu-N bonds of 1.898(5) {\AA}, an N-CuI-N angle of 157.5(3)°, a Se···Se interaction at 3.6237(3) {\AA}, and a very small Se-Cu-Se angle of 78.23(4)°. The different responses resulting from thioether and selenoether coordination to copper in the complexes at hand are being discussed. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Leboschka, Markus and Sieger, Monika and Sarkar, Biprajit and Heck, Juergen and Niemeyer, Mark and Bubrin, Denis and Lissner, Falk and Schleid, Thomas and Zalis, Stanislav and Su, Cheng-Yong and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2245092d5815dde0936d9667df2ce44ae/b_schwederski},
doi = {10.1002/zaac.200900265},
interhash = {61ad9a74532ca927589cbb76f5847098},
intrahash = {245092d5815dde0936d9667df2ce44ae},
issn = {0044-2313},
journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie},
keywords = {alkylselenomethylbenzimidazole alkylselenophenylbenzimidazole alkylselenophenylbenzimidazole;optimized copper methylmethylthiomethylbenzimidazole mol prepn;crystal structure},
number = {13-14},
pages = {2177--2184},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {2-Organoselenomethyl-1H-benzimidazole Complexes of Copper(II) and Copper(I)},
volume = 635,
year = 2009
}