185200-25-3Relevant academic research and scientific papers
Studies on the electronic influence of organoligands. XIII. Synthesis and characterization of 2-functionalized vinyl rhodoximes
Aisa, A. M. Ahmed,Heinemann, Frank W.,Steinborn, Dirk
, p. 1946 - 1952 (2008/10/09)
2-Functionalized vinyl rhodoximes [Rh(dmgH)2 (PPh3)cis/trans-CH=CHZ] ([Rh]-CH=CHZ)1) (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, 31C 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 triphenylphosphine and the 2-phenylmercaptovinyl ligands. Van der Waals interactions exist between the sulfur and the equatorial dimethylglyoximato ligands in the cis complex 1 m. Johann Ambrosius Barth 1996.
