| | 1 | Author
| Dieter Sellmann, Stefan Fünfgelder, Falk Knoch | Requires cookie* | | | Title
| Übergangsmetallkomplexe mit Schwefelliganden, LXXV  | | | | Abstract
| Synthese und Struktur von INi('NHS4)|2 und |N i(Py)2('S2')| * Py; Radikalische Templatalkylierungen von |Ni('S2')2l2~** Transition Metal Complexes with Sulfur Ligands, LXXV* Syntheses and Structure of [Ni('NHS4')]2 and [Ni(Py)2('S2')] • Py; Radical Alkylations of [Ni('S2')2]: ** [N i('N HS4')]2 ('N nS4'2~ = 2,2'-bis(2-m ercaptophenylthio)diethylam ine(2-)) was synthesized from Ni(ac)-, and N a2-' N HS4' and characterized by X-ray structure analysis. In the solid state [N i('N HS4')]2 contains two pseudooctahedral [N i('N HS4')] fragments bridged via thiolate d o nors, in D M F solution at 110 C it dissociates into mononuclear entities. The product o f the template reaction between [Ni('S2')2]2~ ('S2'2-= 1,2-benzenedithiolate) and (BrC\H4)2NH was shown to contain an as yet unidentified by-product in addition to [Ni('NnS4')]2. Pure [N i('N HS4')]2 does not react with pyridine, but the template product forms [N i(Py)2('S2')] which has a square planar coordination geometry with the pyridine rings perpendicular to the N iS2N 2 plane. Investigation o f the template formation o f [N i('N HS4')]2 provided evidence that the reaction o f [Ni('S,')J--with (BrC2H4)^NH involves radicals, suggesting a radical chain reaction m echa nism. | | | |
Reference
| Z. Naturforsch. 46b, 1593—1600 (1991); eingegangen am 13. Mai 1991 | | | |
Published
| 1991 | | | |
Keywords
| Nickel Sulfur Complexes, X -Ray, Template Reaction | | | |
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| default:Reihe_B/46/ZNB-1991-46b-1593.pdf | | | | Identifier
| ZNB-1991-46b-1593 | | | | Volume
| 46 | |
| 2 | Author
| Dieter Sellmann, Stefan Fünfgelder, Falk Knoch, M. Atthias, Moll | Requires cookie* | | | Title
| Übergangsmetallkomplexe mit Schwefelliganden, LXXVI* Redox-und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (N M e4)2 [Ni('S2')2 l und INi('S4-C 3 /)(PM e3)]** Transition M etal Complexes with Sulfur Ligands, LXXVI* Redox and Addition Reactions of Nickel Complexes with M ultidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (N M e ^ fN ^ 'S ^ j] and [Ni('S4-C 3')(PM e3)]* | | | | Abstract
| In order to elucidate specific properties o f nickel sulfur com plexes, redox and addition-elim-ination reactions o f [Ni('OS4')]2, [N i('N HS4')]2, [Ni('S5')], [Ni('S4-C 5')]2 and [Ni('S4-C 3')] were investigated ('OS4'2-= 2,2'-bis(2-m ercaptophenylthio)diethylether(2-), 'N HS4'2~ = 2,2'-bis(2-m ercaptophenylthio)diethylam ine(2-), 'S5'2-= 2,2'-bis(2-mercaptophenylthio)diethylsul-fid e (2 -), 'S4-C 5'2-= 1,5-bis(2-m ercaptophenylthio)pentane(2-), 'S4-C 3'2-= l,3-bis(2-m er-captophenylthio)propane(2-)). Cyclovoltammetry proves the complexes to be redox inactive between -1 .4 and +0.8 V vs. N H E. A bove +0.8 V the complexes are irreversibly oxidized, below -1 , 4 V desalkylation takes place and [Ni('S2')2]2" is formed. An X-ray structure analysis was carried out o f (N M e4)2[Ni('S2'):>], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni('S2')2] m onoanion. The complexes coordinate only phosphines as coligands, but thioether donors simulta neously decoordinate and, dependant o f reaction temperature, m ono-or trisphosphine com plexes are formed. [Ni('S4-C 3')(PM e3)] was characterized by X-ray structure analysis and ex hibits a square pyramidal coordination geometry. | | | |
Reference
| Z. Naturforsch. 46b, 1601—1608 (1991); eingegangen am 13. Mai 1991 | | | |
Published
| 1991 | | | |
Keywords
| Nickel Sulfur Complexes, Redox and Addition Reactions, X-Ray | | | |
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| default:Reihe_B/46/ZNB-1991-46b-1601.pdf | | | | Identifier
| ZNB-1991-46b-1601 | | | | Volume
| 46 | |
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