Thermolysis of bis(trimethylstannyl)diazomethane (1) or bis(tributylstannyl)diazomethane (2) affords the corresponding bis(stannyl)carbodiimides 3-4. Bis(trimethylstannyl)carbodiimide (3) is also obtained at room temperature by palladium-catalyzed isomerization of diazo derivative 1 and is a powerful precursor of elaborated carbodiimides.
Me(3)Sn-N=C=N-R(1) (R(1) = Si(i)Pr(3), SiPh(2)(t)Bu, Ph) reacts with Cp(2)TiCl(2) (Cp = eta(5)-C(5)H(5), or Cp*(2)TiCl(2) (Cp* = eta(5)-C(5)Me(5)) selectively at the Sn-N bond to give the corresponding bis(carbodiimido)titanium complexes (Cp(2)Ti(N=C=N-SiR(3))(2), Cp*(2)Ti(N=C=N-SiR(3))(2), and Cp(2)Ti(N=C=N-Ph)(2)) in moderate to high yields. The structure of Cp(2)Ti(N=C=N-Ph)(2) was determined by X-ray crystallography. Oligomeric complexes were formed by the reaction of Me(3)Sn-N=C=N-X-N=C=N-SnMe(3) (X = -C(6)H(3)Cl-CH(2)-C(6)H(3)Cl-) with Cp*(2)TiCl(2).
Jaeger, L.; Koehler, H.; Brusilovec, A. I., Zeitschrift fur Anorganische und Allgemeine Chemie
作者:Jaeger, L.、Koehler, H.、Brusilovec, A. I.、Skopenko, V. V.
DOI:——
日期:——
Free-radical addition of trimethyltin hydride to dienes
作者:Richard H. Fish、Henry G. Kuivila、Irene J. Tyminski