Turning a New Leaf on Metal-TMC Chemistry: NiII(TMC) Acetylides

• Published in: Inorganic chemistry Vol. 54; no. 20; pp. 10058 - 10064
• Main Authors: Tyler, Sarah F, Natoli, Sean N, Vlaisavljevich, Bess, Fanwick, Phillip E, Ren, Tong
• Format: Journal Article
• Language: English
• Published: American Chemical Society 19.10.2015
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.5b01883

Novel [Ni­(TMC)­CCY]+-type compounds 1–4 [TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; Y = SiMe3 (1), Si i Pr3 (2), Ph (3), and C2H (4)] have been synthesized and characterized. Single-crystal X-ray diffraction studies revealed that these compounds adopt a distorted square-pyramidal geometry, with the acetylide ligand occupying the apical position and a RSRS isomer for the TMC ligand. The room temperature magnetic properties of 1–4 are consistent with an S = 1 ground state, as corroborated by CASSCF and density functional theory calculations, which indicate that the singly occupied molecular orbitals are d z 2 and d x 2–y 2 .