Turning a New Leaf on Metal-TMC Chemistry: NiII(TMC) Acetylides
† Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States
‡ Department of Chemical & Biomolecular Engineering, University of California, Berkeley, California 94720,United States
Inorg. Chem., Article ASAP
DOI: 10.1021/acs.inorgchem.5b01883
Publication Date (Web): September 28, 2015
Copyright © 2015 American Chemical Society
*E-mail: tren@purdue.edu.
Abstract
Novel [Ni(TMC)C≡CY]+-type compounds 1–4 [TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; Y = SiMe3 (1), SiiPr3 (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 dz2 and dx2–y2.
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