Chemical Transformations of [Pd(OOCMe)4Mn] in the Reactions with 1,10-Phenanthroline and Pivalic Acid

Abstract

A series of new Pd–Mn bimetallic acetate and pivalate complexes were synthesized and structurally characterized. The starting [Pd(OOCMe)₄Mn] complex reacts with N‑donor ligands such as 1,10-phenanthroline (phen) to give [Pd(OOCMe)₄Mn(phen)]⋅MeCN (I) (CCDC no. 2217716). The replacement of acetate bridges in the heterometallic Pd–Mn carboxylate complexes with pivalate bridges was investigated. It was shown that complete replacement of all acetate bridges with pivalate ones can occur both in heterometallic complex I, which contains a ligand coordinated to the second metal atom, to give the compound [Pd(Piv)₄Mn(phen)]⋅C₆H₆ (II) (CCDC no. 2217717), structurally related to the initial acetate complex, and in the acetate complex [Pd(OOCMe)₄Mn]. The heterometallic co-crystallized pivalate [Pd(Piv)₄Mn⋅2HPiv] (III) (CCDC no. 2217718) formed in the latter case can react with 5-nitro-1,10-phenanthroline to give the complex [Pd(Piv)₄Mn(Nphen)] (IV) (CCDC no. 2217719).