Parvin Nasrina, Pal Shiv, Khan Shabana, Das Shubhajit, Pati Swapan K, Roesky Herbert W
Department of Chemistry, Indian Institute of Science Education and Research , Dr. HomiBhabha Road, Pashan, Pune 411 008, India.
New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research , Jakkur, Bangalore, 560 064, India.
Inorg Chem. 2017 Feb 6;56(3):1706-1712. doi: 10.1021/acs.inorgchem.6b02833. Epub 2017 Jan 13.
Silylene-S-thione [PhC(NtBu)Si(═S)N(SiMe)] (2) and silylene-Se-selone [PhC(NtBu)Si(═Se)N(SiMe)] (3) compounds were prepared from the silylene [PhC(NtBu)SiN(SiMe)] (1) with 1 equiv of 1/8 S and 1 equiv of Se powder, respectively, in high yields. Furthermore, compounds 2 and 3 reacted with CuCl and CuBr and yielded [{PhC(NtBu)}Si(═S→CuX)N(SiMe)] (X = Cl (4), Br (5)) and [{PhC(NtBu)}Si(═Se→CuX)N(SiMe)] (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)}Si{N(SiMe)}]CuX (X = Cl (8), Br (9)). The latter route avoids the preparation of the highly reactive silylene chalcogenones. For comparison purposes the silylene PhC(NtBu)SiN(SiMe) in 2 and 3 was replaced by NHC (1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) (10). The resulting products NHC═S (thione 11) and NHC═Se (selenone 12) react with CuBr and lead to the expected complexes (NHC═S→CuBr) (13) and (NHC═Se→CuBr) (14). However, unlike silylene complexes, 13 and 14 cannot be prepared by reacting NHC-CuBr (15) with chalcogens.
硅烯 - S - 硫酮[PhC(NtBu)Si(═S)N(SiMe)]（2）和硅烯 - Se - 硒酮[PhC(NtBu)Si(═Se)N(SiMe)]（3）化合物分别由硅烯[PhC(NtBu)SiN(SiMe)]（1）与1当量的1/8 S和1当量的Se粉末制备而成，产率很高。此外，化合物2和3与CuCl和CuBr反应，分别生成[{PhC(NtBu)}Si(═S→CuX)N(SiMe)]（X = Cl（4），Br（5））和[{PhC(NtBu)}Si(═Se→CuX)N(SiMe)]（X = Cl（6），Br（7））。配合物4 - 7也可以通过硫和硒与相应的硅烯铜配合物[{PhC(NtBu)}Si{N(SiMe)}]CuX（X = Cl（8），Br（9））直接反应得到。后一种方法避免了制备高反应活性的硅烯硫属酮。为了进行比较，2和3中的硅烯PhC(NtBu)SiN(SiMe)被NHC（1,3 - 双（2,6 - 双（二苯基甲基）- 4 - 甲基苯基）咪唑 - 2 - 亚基）（10）取代。所得产物NHC═S（硫酮11）和NHC═Se（硒酮12）与CuBr反应，生成预期的配合物（NHC═S→CuBr）（13）和（NHC═Se→CuBr）（14）。然而，与硅烯配合物不同，13和14不能通过NHC - CuBr（15）与硫属元素反应制备。
