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In the crystal structure of 1[Ln2(Mblm)4(BbIm, 1,2) each Ln atom (Ln, Ho, Yb) is coordinated, by an end-on and a μ2bridging S atom of 1,3-chelating 2-mercaptobenzimidazolate anions, as well as a 1,4-chela.ting 2,2'-bibenzimidazola.te dianion. Pairs of the resulting pentagonal bipyramidal LnS3N4 coordination polyedra are edge sharing via common S atoms. These dirneric units are linked to strands via the 2,2'-bibenzimidazolate dianions. For detailed data on the single-crystal Xray investigations and presentations of the crystal structure of isotypic 1 and. 2: see Supporting Information. Further information was deposited, at the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB2 IEZ, UK (Fax: +44-1223336033 or E-mail: deposit@ccdc.cam.ac.uk) and may be requested by citing the deposition numbers CCDC7.16039 (for 1, 716041 for 2, the names of the authors and the literature citati
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In contrast numerous transition metal complexes were presented with this ligand until recently, e.g.;
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In contrast numerous transition metal complexes were presented with this ligand until recently, e.g.;
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Referring experiments carried out directly from benzimidazole melts together with Ln elements gave no in situ formation of 2,2'-bibenzimidazole but a previously unknown high-temperature form of benzimidazole itself. It forms on. the surface of the lantlianide metals. We also determined, the crystal structure of this ß-1-H--benzimidazole (5, It can be distinguished from the room temperature a-form by a closer overall packing see Supporting Information and CCDC-716038
-
Referring experiments carried out directly from benzimidazole melts together with Ln elements gave no in situ formation of 2,2'-bibenzimidazole but a previously unknown high-temperature form of benzimidazole itself. It forms on. the surface of the lantlianide metals. We also determined, the crystal structure of this ß-1-H--benzimidazole (5). It can be distinguished from the room temperature a-form by a closer overall packing (see Supporting Information and CCDC-716038).
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CCDC-716040 and the Supporting Information contain detailed crystallographic data for 3: C63H43LaN18, M, 1.191.1 gmol-1, crystal, dimensions 0.1 X 0.08 X 0.03 mm; orthorhombic, space group C2221 (No. 20, a, 1673.6(3) pm, b, 1513.5(3) pm, c, 2243.9(4) p.m, T, 200 K, Z, 4, V, 5683,8(2) X 106 pm3, pcálc±, 1.392 g cm-3, 20max, 47.12°, diffractometer Nonius Kappa CCD, Ω-Scan with An, 0,9°, radiation Mo-Ka, wave length γ, 0.71073 ̊, Flack-X Parameter 0,00(6, 21191 measured reflections, 4192 independent reflections, 3614 reflections with I>20[I, refined parameters 372. R 1, 0.0541 for 36.14 with I>20[I, wR2, 0.0953 for all 4192 independent reflections; remaining electron density: +1.45/-0.68 e pm 106
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6).
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67
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85152985101
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The negative charges of the square antiprismatic ions of 3 are compensated by benzimidazolium cations in a ratio of 1:1 resulting in the overall formula (Bim.H2, La(BbimH)4] for this salt like compound. As no benzimidazole was added, to the reaction, the cations also derive from the C-S bond cleavage but with subsequent protonation instead of recombination to bibenzimidazole. The benzimidazolium cations are non-coordinating. Anionic benzimidazolates are not known for lanthanides today. The cationic character is evident in a reduction of the aromatic character of the ring system, by elongating C-N distances in the imidazole part. This behaviour resembles pyridylbenzimidazolium cations that also compensate the charges of corresponding square antiprismatic Ln-pyridylbenzimidazolate anions.[6c] Further information on the crystal structure of 3 can be deduced, from the Supporting Information
-
[6c] Further information on the crystal structure of 3 can be deduced, from the Supporting Information.
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85152988197
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On the steric demand of N-heterocycles such as substituted aminopyridinato ligands in complexes see Kempe et al. for the example of 1,3-chelation: a R. Kempe, Eur. J. Inorg. Chem. 2003, 791-803;
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On the steric demand of N-heterocycles such as substituted aminopyridinato ligands in complexes see Kempe et al. for the example of 1,3-chelation: a) R. Kempe, Eur. J. Inorg. Chem. 2003, 791-803;
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Known are complexes of the Ln elements that are acetylbenzopyranone substituted, on the S atom of 2-merca.ptobenzimidazole. Because of the oxophilicity of the lanthanid.es they are coordinated via O and not S atoms, accordingly: K. B. Gudasi, T. R. Goudar, J. Indian Chem. Soc. 1997, 74, 786-788.
-
Known are complexes of the Ln elements that are acetylbenzopyranone substituted, on the S atom of 2-merca.ptobenzimidazole. Because of the oxophilicity of the lanthanid.es they are coordinated via O and not S atoms, accordingly: K. B. Gudasi, T. R. Goudar, J. Indian Chem. Soc. 1997, 74, 786-788.
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