94333-12-7Relevant academic research and scientific papers
Carbene complex formation versus cyclometallation from a phosphoryl-tethered methanide ruthenium complex
Feichtner, Kai-Stephan,Gessner, Viktoria H.,Paa?en, Maurice,Papp, Florian,Schmidt, Michelle
, (2020)
An oxophosphoryl-substituted methanide ligand system for transition metal complexes has been synthesized and isolated as the sodium salt Na[Ph2P(O)–C(H)–SO2Ph]. This ligand features structural components known to enable the isolation of nucleophilic late transition metal carbene complexes. The corresponding ruthenium(cymene) chlorido complex was readily available by simple salt metathesis reaction. However, in contrast to previously reported thio- and iminophosphoryl-tethered ligand systems, dehydrohalogenation of the chlorido complex led to the formation of a cyclometallated ruthenium complex instead of the carbene complex. All compounds have been characterized in solution and solid state. Additional density functional theory (DFT) studies have been performed to elucidate the mechanism of the observed cyclometallation and to shed light on the effects of different P(V) groups in the ligand system on the stability and reactivity of the corresponding carbene complexes. The calculations show that the weaker coordination of the P[dbnd]O compared to the P[dbnd]S or P[dbnd]N moiety is responsible for the more facile C–H activation.
Synthesis and evaluation of photophysical and electrochemical properties of vinyl chalcogenide derivatives of phenothiazines
Dilelio, Marina Cardoso,Kaufman, Teodoro S.,Iglesias, Bernardo Almeida,Silveira, Claudio C.
, (2021/12/07)
The Wittig-Horner mediated syntheses of phenothiazines carrying vinylsulfide and vinylselenide motifs attached to the aromatic ring(s) or connected to the central nitrogen atom of the heterocycle, and the subsequent study of their photophysical and electr
Synthesis and electronic structure of carbene complexes based on a sulfonyl-substituted dilithio methandiide
Becker, Julia,Gessner, Viktoria H.
, p. 1310 - 1317 (2014/04/03)
The application of a sulfonyl-substituted dilithio methandiide in the synthesis of carbene complexes was examined. In all cases, the metal carbon interaction was found to be highly polar with only small π-contribution. Hence, the stability of these complexes was found to greatly rely on the coordination ability of the side-arms supporting the metal carbon interaction. As such, the sulfonyl moiety allowed the isolation of a carbene complex with the oxophilic zirconium, which is the first of its kind bearing no (bis)phosphonium ligand framework. On the contrary, complexes with the late transition metals ruthenium and palladium were found to be more labile due to the facile decoordination of the sulfonyl moiety. This results in the opening of a reactive coordination site at the metal center and hence in further reactions such as cyclometalation or sulfur transfer from the thiophosphoryl moiety to the carbenic carbon atom.
