| 1 | Author
| AndreasF. Stange, Eberhard Waldhör, Michael Moscherosch, Wolfgang Kaim | Requires cookie* | | Title
| Variable Structure of the Cu2S2 Core in Doubly Thiolate-Bridged Dicopper(I) Complexes. An X-Ray Crystallographic, Electrochemical and EPR Study of (dmp)2 (o-CH3 C6H4S)2Cu2 , dmp = 2,9-Dimethyl-l,10-phenanthroline, and a Comment on the Nature of Phenanthroline-Containing "Cu(0)" Complexes  | | | Abstract
| The molecular and crystal structure of the dicopper(I) complex (dm p)2(M-o-CH3C6H4S)2Cu2 (1), dmp = 2,9-dim ethyl-l,10-phenanthroline, has been deter mined. With Cu/S/Cu and S/Cu/S bond angles between 80 and 100°, the planar structure of the central CuSCuS four-membered ring is much more symmetric for 1 as compared to the analogous complex 2 of unsubstituted 1,10-phenanthroline which has a folded Cu2S2 core with bond angles between 67 and 108°. This result illustrates a considerable structural flexi bility of the LCu(m-SR)2CuL entity which is being discussed as a possible model for CuA centers of cytochrome c oxidase or nitrous oxide reductase. Oxidation of both com plexes 1 and 2 remains irreversible even at cyclovoltammetric scan rates o f 1 V/s. However, the methyl substitution in complex 1 causes increased reversibility of the electronically coupled dmp-based reduction processes. Accordingly, the EPR spectrum of l -* is characterized by hyper-fine splitting from dmp--and a relatively small 63 " Cu coupling of 0.53 mT. The stabilization of 2,9-disubstituted 1,10-phenanthroline radical anions by coordination to Cu(I) is also dem onstrated by detection of a single broad EPR line at g 2.0028 for the formal "C u(0)" complex Cu(dpp)2 = CuI(dpp_-)(dpp), dpp = 2,9-diphenyl-l,10-phenanthroline. While the EPR signal of Cu(dpp)2 loses intensity on cooling, possibly due to dimerization and spin-pairing, the distorted tetrahedral configuration with essential orthogonal arrangement of dpp jz systems seem s to disfavour an intramolecular electron hopping. | | |
Reference
| (Z. Naturforsch. 50b, 115—122 [1995]; received July 25 1994) | | |
Published
| 1995 | | |
Keywords
| Crystal Structure, Copper Complexes, Sulfur Ligands, 1, 10-Phenanthrolines, EPR Spectra | | |
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| default:Reihe_B/50/ZNB-1995-50b-0115.pdf | | | Identifier
| ZNB-1995-50b-0115 | | | Volume
| 50 | |
2 | Author
| RajK. Bansal, Neelam Gandhi, A. Schmidpeter, K. Karaghiosoff | Requires cookie* | | Title
| Synthesis of [l,2,4,3]Triazaphospholo[l,5-a]pyridines+  | | | Abstract
| Condensation o f 1,2-diaminopyridinium iodides with tris(dimethylamino)phosphine gives [l,2,4,3]triazaphospholo[l,5-a]pyridines 2a-d. Diethylamine adds to the N=P bond o f 2a, b only if the phosphorus is oxidized at the same time. Hydrolysis of 2 a opens the triazaphos-phole ring at its 2,3-bond. | | |
Reference
| Z. Naturforsch. 50b, 558 (1995); received October 21 1994 | | |
Published
| 1995 | | |
Keywords
| l, 3-Diaza-2-phosphaindolizines, NM R Spectra, Mass Spectral Fragmentation, Hydrolysis, 1, 2-Addition Reactions | | |
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| default:Reihe_B/50/ZNB-1995-50b-0558.pdf | | | Identifier
| ZNB-1995-50b-0558 | | | Volume
| 50 | |
3 | Author
| Hans Bock, Sabine Nick, Christian Näther, Wolfgang Bensch | Requires cookie* | | Title
| Wechselwirkungen in Kristallen, 63 [1, 2]  | | | Abstract
| Kristallisation und Strukturbestimmung von 1,2-Dimesitoylbenzol und von Bis(hydrogen-l,2-dimesitoylbenzol)-dinatrium-bis(ethylendiamin) Interactions in Crystals, 63 [1, 2] Crystallization and Structure Determ ination of 1,2-Dimesitoylbenzene and of Bis(hydrogen-l,2-dimesitoylbenzene)-disodium-bis(ethylendiamine) | | |
Reference
| Z. Naturforsch. 50b, 605 (1995); eingegangen am 18. August 1994 | | |
Published
| 1995 | | |
Keywords
| 1, 2-Dimesitoylbenzene, Radical A nion Sodium Salt, Single Crystal Structures, M N D O Calculations | | |
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| default:Reihe_B/50/ZNB-1995-50b-0605.pdf | | | Identifier
| ZNB-1995-50b-0605 | | | Volume
| 50 | |
4 | Author
| Z. Naturforsch | Requires cookie* | | Title
| Synthese und Charakterisierung von 1,3,5-Hexahydrotriazin-Komplexen des Mo° und Movl  | | | Abstract
| Organo-substituted 1,3,5-hexahydrotriazine com plexes of the type (R N C H 2)3M o(C O)3 (R = CFI3, / -C 3 H 7 and CH2C6H 5) are obtained by ligand displacement from 7 6-C7H 8M o(C O)3 in high yields. These products have been characterized by 'H. 13C, 95Mo NM R, IR as well as mass spectroscopy and contain an electron-rich M o(C O)3 center bonded to the 1,3,5-hexahydrotriazine 6 e donor via three M o -N bonds. Oxidation o f the Mo° com plex l,3,5-(C H 3N CH 2)3M o(C O)3 with H20 2 under carefully controlled conditions allows iso lation of 1,3,5-(CH3N C H 2) 3M o 0 3 containing a M ovl center. Chemical and spectroscopic properties o f these com plexes are compared with those o f related Mo com plexes with neutral macrocyclic ligands containing N 3 donor sets. | | |
Reference
| Z. Naturforsch. 50b, 1038—1044 (1995); eingegangen am 30. Dezem ber 1994 | | |
Published
| 1995 | | |
Keywords
| 1, 3, 5-Hexahydrotriazines, Carbonyl Complexes, O xo Complexes, R edox Chemistry, Multinuclear NM R Spectra | | |
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| default:Reihe_B/50/ZNB-1995-50b-1038.pdf | | | Identifier
| ZNB-1995-50b-1038 | | | Volume
| 50 | |
5 | Author
| Neda, Michael Farkens, Holger Thönnessen, PeterG. Jones, Reinhard Schmutzler | Requires cookie* | | Title
| Zur Chemie der l,3,5-Triaza-2-phosphorinan-4,6-dione. Teil X*. Umsetzungen von 2-Hydro  | | | Abstract
| l,3,5-trimethyl-l,3,5-triaza-2-oxo-2A4-phosphorinan-4,6-dion mit Triazin-Derivaten sowie mit einigen Aldehyden Chemistry of the l,3,5-Triaza-2-phosphorinan-4,6-diones. Part X*. Reactions of 2-H ydro-1,3,5-trim ethyl-1,3,5-triaza-2-oxo-2A4-phosphorinan-4,6-dione with Triazine Derivatives and with Some Aldehydes Ion | | |
Reference
| Z. Naturforsch. 50b, 1833—1 (1995); eingegangen am 8. Mai 1995 | | |
Published
| 1995 | | |
Keywords
| 1, 3, 5-Trimethyl-Substituted l, 3, 5-Triaza-2A 4 -phosphorinan-4, 6-diones, NM R Spectra, Mass Spectra, X-Ray | | |
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| default:Reihe_B/50/ZNB-1995-50b-1833.pdf | | | Identifier
| ZNB-1995-50b-1833 | | | Volume
| 50 | |
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