Synthesis und Reaktivität von Dimethylaminoalkylidenaminooxy-arsinen

Synthesis and Reactivity of Dimethylaminoalkylideneaminooxiarsines The reactions of As[N(CH₃)₂]₃ with oximes result in the formation of the oximates [(CH₃)₂N]₂AsONCRR′, (CH₃)₂N As(ONCRR′)₂ and As(ONCRR′)₃. The eleavage of the As-N-bond with alcohols, thiols and diols are described. The reactions of CH₃As[N(CH₃)₂]ONCRR′ with water, amine and alcohols are examined. IR-and ¹H-NMR-spectral data are presented.     

Koordination und Reaktivität von Sulfinylimiden RNSO in Cyclopentadienyldicarbonylmangan‐Komplexen

Coordination and Reactivity of Sulfinylimides RNSO in Cyclopentadienyldicarbonylmanganese Complexes The coordination behaviour of sulfinylimides RNSO (R = SiMe₃, Ph) towards CpMn(CO)₃ (Cp = C₅H₅, C₅H₄CH₃) has been studied. Under total exclusion of water the substitution products CpMn(CO)₂{S(O)NR} ( 2 a , b , 2 ′ a , b ) with μ¹‐S‐linkage are formed. In the presence of water, however, the SO₂ complexes 3 , 3 ′ as iminofree hydrolysis products are obtained. There are only spectroscopic indications for the directed hydrolytic conversion of the silyl derivatives 2 a , 2 ′ a into the unstable HNSO complexes 4 , 4 ′ by cleavage of the Si–N‐bond and retention of the cumulene moiety. The molecular structures of π‐C₅H₅Mn(CO)₂{S(O)NSiMe₃} ( 2 a ) and π‐C₅H₄CH₃Mn(CO)₂SO₂ ( 3 ′) were elucidated by single crystal X‐ray analyses.