Synthese von Erdalkalimetallocenen aus Erdalkalimetall- bis[bis(trimethylsilyl)amid] und 6-Methyl-6-phenylfulven / Synthese von Erdalkalimetallocenen aus Erdalkalimetallbis[ bis(trimethylsilyl)amid] und 6-Methyl-6-phenylfulven Synthesis of Alkaline Earth Metallocenes from Alkaline Earth Metal Bis[bis(trimethylsilyl)amide] and 6 -Methyl-6 -phenylfulvene

Abstract

The transmetalation of bis[bis(trimethyIsilyl)amino]stannylene in tetrahydrofuran with the alkaline earth metals yields the bis(tetrahydrofuran) adducts of calcium (1a), strontium (1b) and barium bis[bis(trimethylsilyl)amide] (1c). The metalation of 6-methyl-6-phenylfulvene with 1a, 1b and 1c gives 1,1′-bis(l-phenyl-ethen-l-yl)calcocene 2a, -strontocene 2b and -barocene 2c, respectively. The reaction of 1b with equimolar amounts of 6-methyl-6-phenylfulvene and acetophenone leads to the formation of bis[μ-[η 5 -1-(3-hydroxy-1-methyl-1,3-diphenyl-2- propen-1-yl )-2,4-cyclo -pentadien-l-yl](2-)-C,O:O]tetrakis(tetrahydrofuran-O)distrontium 3. The metathesis reaction of 2a with YCl 3 and SnCl 2 yields the corresponding yttrocenechloride 4 and stannocene 5. Crystallographic data of 1a: monoclinic, P2 1 /c, a = 841.6(4), b = 1936.9(6), c = 1938.0(10) pm, β = 100.84(4)°, Z = 4, wR 2 =0,1199); 1b: orthorhombic, Pbca, a = 1924.8(4), b = 1747.8(3), c = 1930.1(4) pm, Z = 8, wR 2 = 0.1248; 3: monoclinic, P2 1 /c, a = 1230.42(11), b = 1343.08(11), c = 1597.34(14) pm, β = 104.610(7)°, Z = 4, wR 2 = 0.0980.