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• W1990232004 abstract "2-Funktionalisierte Vinylrhodoxime [Rh(dmgH)2(PPh3)cis/trans-CH  CHZ] ([Rh]CH  CHZ) Die Komplexe 1 sind durch Elementaranalyse sowie 1H-, 13C- und 31P-NMR-spektroskopisch charakterisiert. Die Größe der Kopplungskonstanten 1J(103Rh, 31P) läßt nur einen geringen Einfluß von Z auf den (NMR) trans-Einfluß des Vinylliganden CH = CHZ erkennen. Die Molekülstrukturen von cis-[Rh]CH = CHSPh (1 m) und trans-[Rh]CH = CHSPh (1 d) zeigen eine verzerrt oktaedrische Koordination von Rh mit einer gegenseitigen trans-Stellung von Triphenylphosphin und dem 2-Phenylmercaptovinyl-liganden. In der cis-Verbindung 1 m bestehen van der Waals Kontakte zwischen dem Schwefel und den äquatorialen Dimethylglyoximatoliganden. Studies on the Electronic Influence of Organoligands. XIII. Synthesis and Characterization of 2-Functionalized Vinyl Rhodoximes 2-Functionalized vinyl rhodoximes [Rh(dmgH)2 (PPh3)cis/trans-CH = CHZ] ([Rh]CH = CHZ)) (1) can be prepared with a wide variation of the substituent Z (cis: OEt (1 a), OPh (1 b), Cl (1 c), Me (1 j), Ph (1 k), SMe (1 l), SPh (1 m); trans: SPh (1 d), Me (1 e), Ph (1 f), CMe3 (1 g), SiMe3 (1 h)) by oxidative addition of XCH = CHZ and/or by nucleophilic addition of HCCZ and Me3SiCCZ, respectively, to [Rh]−. 1 a is converted to [Rh]CH2CHO (2) already in a weakly acid medium. 1 l is isomerized to trans-[Rh]CH = CHSMe (1 n) in the presence of acids. The complexes 1 are characterized by microanalysis and by 1H, 13C and 31P NMR spectroscopy. The magnitude of the coupling constants 1J(103Rh, 31P) reveals only a small effect of Z on the (NMR) trans influence of the vinyl ligands CH = CHZ. The molecular structures of cis-[Rh]CH = CHSPh (1 m) and trans-[Rh]CH = CHSPh (1 d) show a distorted octahedral coordination of Rh with a mutual trans position of triphenyl-phosphine and the 2-phenylmercaptovinyl ligands. Van der Waals interactions exist between the sulfur and the equatorial dimethylglyoximato ligands in the cis complex 1 m." @default.
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• W1990232004 date "1996-11-01" @default.
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• W1990232004 title "Untersuchungen zum elektronischen Einflu� von Organoliganden. XIII. Synthese und Charakterisierung von 2-funktionalisierten Vinylrhodoximen" @default.
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• W1990232004 doi "https://doi.org/10.1002/zaac.19966221122" @default.
• W1990232004 hasPublicationYear "1996" @default.
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