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Herein we report the first structural characterization of a Pt(iv)-kappa(3)-terpyridine species, [Pt((t)Bu(3)tpy)Cl(3)][AuCl(2)], which can be prepared by oxidation with [AuCl(4)](-). The syntheses and characterization of [Pt((t)Bu(3)tpy)Cl(3)]Cl ((t)Bu(3)tpy is 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine), as well as the platinum(ii) complexes [Pt((t)Bu(3)tpy)Cl]Cl and [Pt((t)Bu(3)tpy)Cl][AuCl(2)] are reported.

The crystal structure of the title compound, [PtBr(C(15)H(11)N(3))][AuBr(2)]·(CH(3))(2)SO, exhibits infinite chains of {PtAuPt}(∞) metallophilic inter-actions along the b axis. Two cations and one anion stack in a trimer with a unique Pt⋯Au distance of 3.3361 (5) Å and Pt⋯Pt contacts of 3.4335 (6) Å. The remaining [AuBr(2)](-) anion forms no close contacts.

In the title compound, [PtI(C(15)H(11)N(3))][AuI(2)], the [PtI(terpy)](+) cations (terpy is 2,2':6',2''-terpyridine) stack in pairs about inversion centers through Pt...Pt interactions of 3.5279 (5) A. The [AuI(2)](-) anions also exhibit pairwise stacking, with Au...I distances of 3.7713 (5) A. The [PtI(terpy)](+) cations and [AuI(2)](-) anions aggregate forming infinite arrays of stacked ...([[PtI(terpy)](+)...[PtI(terpy)](+)]...[[AuI(2)](-)...[AuI(2)](-)])... units.