Abstract
New direct syntheses of [Pt(trpy)(NCCH 3)](CF 3SO 3) 2 2 (where trpy = 2,2′:6′,2′′-terpyridine) and [Pt( tBu 3-trpy)(NCCH 3)](CF 3SO 3) 2 3 (where tBu 3-trpy = 4,4′,4″-tri- tert-butyl-2,2′:6′,2″-terpyridine) via the displacement of acetonitrile from [Pt(NCCH 3) 4](CF 3SO 3) 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 PPh 3, CN-Xyl, and CN- tBu, dealkylation of TM4 occurred to afford [Pt(trpy)(CN)](CF 3SO 3) 6. The structures of [Pt(trpy)L] 2+ dications show little intermolecular interactions in the solid state, with the exception of the tBu 3-trpy complex 3 which exists as head-to-tail dimers with a Pt–Pt distance of 3.29 Å. The cyano product 6 was found to stack in infinite chains of cations with a Pt–Pt distance of 3.45 Å.
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