Synthesis and structure of a bis-trifluoromethylthiolate complex of nickel

Reaction of [(dippe)NiI2] (dippe = 1,2-bis(diisopropylphosphino)ethane) with excess [NMe4][SCF3] led to the formation of [(dippe)Ni(SCF3)2] (1) in 92% isolated yield. Complex 1 has been structurally characterized, and the data provides the first experimentally determined bond parameters of a nickel–trifluoromethylthiolate complex. The molecule lies on a two-fold axis, with nickel-phosphorus bonds of 2.1828(4) Å and nickel-sulfur bonds of 2.2395(4) Å. Density functional theory (DFT) calculations predict that the highest occupied molecular orbital (HOMO) is sulfur-centered and the lowest unoccupied molecular orbital (LUMO) is nickel-centered.

Graphical abstractReaction of [(dippe)NiI2] (dippe = 1,2-bis(diisopropylphosphino)ethane) with excess [NMe4][SCF3] led to the formation of [(dippe)Ni(SCF3)2] (1) in 92% isolated yield. Complex 1 has been structurally characterized, and the data provides the first experimentally determined bond parameters of a nickel-trifluoromethylthiolate complex. The molecule lies on a two-fold axis, with nickel–phosphorus bonds of 2.1828(4) Å and nickel–sulfur bonds of 2.2395(4) Å. Density functional theory (DFT) calculations predict that the highest occupied molecular orbital (HOMO) is sulfur-centered and the lowest unoccupied molecular orbital (LUMO) is nickel-centered.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Reaction of [(dippe)NiI2] with excess [NMe4][SCF3] led to the formation of [(dippe)Ni(SCF3)2]. ► [(dippe)Ni(SCF3)2] has been structurally characterized. ► Density functional theory calculations predict that the highest occupied molecular orbital of [(dippe)Ni(SCF3)2] is sulfur-centered and the lowest unoccupied molecular orbital is nickel-centered. ► Charge distributions on a metal–SCF3 complex are much different than a metal–OCF3 one.