Unique Approach to Copper(I) Silylene Chalcogenone Complexes
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Silylene-S-thione [PhC(NtBu)2Si(S)N(SiMe3)2] (2) and silylene-Se-selone [PhC(NtBu)2Si(Se)N(SiMe3)2] (3) compounds were prepared from the silylene [PhC(NtBu)2SiN(SiMe3)2] (1) with 1 equiv of 1/8 S8 and 1 equiv of Se powder, respectively, in high yields. Furthermore, compounds 2 and 3 reacted with CuCl and CuBr and yielded [{PhC(NtBu)2}Si(S→CuX)N(SiMe3)2] (X = Cl (4), Br (5)) and [{PhC(NtBu)2}Si(Se→CuX)N(SiMe3)2] (X = Cl (6), Br (7)), respectively. Complexes 4–7 can also be obtained from the direct reaction of sulfur and selenium with the corresponding silylene copper complexes [{PhC(NtBu)2}Si{N(SiMe3)2}]2Cu2X2 (X = Cl (8), Br (9)). The latter route avoids the preparation of the highly reactive silylene chalcogenones. For comparison purposes the silylene PhC(NtBu)2SiN(SiMe3)2 in 2 and 3 was replaced by NHC (1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) (10). The resulting products NHCS (thione 11) and NHCSe (selenone 12) react with CuBr and lead to the expected complexes (NHCS→CuBr) (13) and (NHCSe→CuBr) (14). However, unlike silylene complexes, 13 and 14 cannot be prepared by reacting NHC-CuBr (15) with chalcogens.
