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The thf-complexed silanimine  t Bu 2 Si=N–Si t-  Bu 3 ·thf ( 1 (thf); monoclinic, space group  C 2/ c ) was prepared by the reaction of 1 equivalent of  t Bu 2 SiClN 3  with 1 equivalent of Na[Si t Bu 3 ] in Bu 2 O and subsequent addition of thf. By heating a benzene solution over a period of 11 d –140 °C,  1 (thf) slowly released the thf donor to form the uncomplexed silanimine  1 . However, under these conditions the silanimine  1  is unstable and is thermolized to give the ene reaction product of  1  with isobutene, H 2 C=C(CH 2 Si t Bu 2 –NH–Si t Bu 3 ) 2 . By contrast, the thermolysis reaction of Me 2 Si=N–Si t Bu 3 ·thf yielded the silanimine dimer (Me 2 SiNSi t Bu 3 ) 2  in 51 % and the vinyl ether Me 2 Si(OCH=CH 2 )NHSi t Bu 3  in 49 % yield.

Crystal structure and thermal decomposition of the Silanimine t Bu 2 Si=N-Si t Bu 3 ·thf