title: Unique Approach to Copper(I) Silylene Chalcogenone Complexes.
abstract: 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 S8and 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)2in 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.
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research , Dr. HomiBhabha Road, Pashan, Pune 411 008, India.
authors.forename: Nasrina
authors.initials: N
authors.lastname: Parvin
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research , Dr. HomiBhabha Road, Pashan, Pune 411 008, India.
authors.forename: Shiv
authors.initials: S
authors.lastname: Pal
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research , Dr. HomiBhabha Road, Pashan, Pune 411 008, India.
authors.forename: Shabana
authors.identifier: http://orcid.org/0000-0002-6844-3954
authors.initials: S
authors.lastname: Khan
authors.affiliation: New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research , Jakkur, Bangalore, 560 064, India.
authors.forename: Shubhajit
authors.initials: S
authors.lastname: Das
authors.affiliation: Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research , Jakkur, Bangalore, 560 064, India.
authors.forename: Swapan K
authors.initials: SK
authors.lastname: Pati
authors.affiliation: Institute of Inorganic Chemistry, University of Göttingen , Tammannnstrasse 4, Göttingen 37077, Germany.
authors.forename: Herbert W
authors.initials: HW
authors.lastname: Roesky