New direct syntheses of [Pt(trpy)(NCCH3)](CF3SO 3)2 2 (where trpy = 2,2′:6′,2′′- terpyridine) and [Pt(tBu3-trpy)(NCCH3)](CF 3SO3)2 3 (where tBu3-trpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine) via the displacement of acetonitrile from [Pt(NCCH3)4] (CF3SO3)2 have been developed. The synthetic utility of 2 was investigated in reactions with triphenylphosphine (PPh 3), 2,6-dimethylphenyl isocyanide (CN-Xyl), 2,5-dimethyl-2,5- diisocyanohexane (TM4), and tert-butyl isocyanide (CN-tBu). Whereas the expected substitution products were observed for reactions with PPh3, CN-Xyl, and CN-tBu, dealkylation of TM4 occurred to afford [Pt(trpy)(CN)](CF 3SO3) 6. The structures of [Pt(trpy)L]2+ dications show little intermolecular interactions in the solid state, with the exception of the tBu3-trpy complex 3 which exists as head-to-tail dimers with a Pt-Pt distance of 3.29 . The cyano product 6 was found to stack in infinite chains of cations with a Pt-Pt distance of 3.45 .
Bibliographical noteFunding Information:
This research was supported, in part, by the following programs of the National Science Foundation : Research Site for Educators in Chemistry program at the University of Minnesota , Twin Cities ( award #0113894 ); Major Research Instrumentation program ( award #0722669 ); and the Louis Stokes Alliance for Minority Partnership (LSAMP) initiative ( award #0703356 ). T.M.P. acknowledges the following: Dr. Daron Janzen for helpful discussions on the crystallographic data; The Supercomputing Institute of the University of Minnesota; University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research; and the UMM Division of Science and Mathematics.
- Platinum complexes
- Terpyridine complexes
- X-ray crystal structures