Reactions of Tris(o-<i>N</i>,<i>N</i>-dimethylaminobenzyl)cerium(III) with Oxidizing Agents, Dichalcogenides, and a Thiophosphinic Amide Ligand

Reactions of a cerium(III) o-<i>N</i>,<i>N</i>-dimethylaminobenzyl (DMAB) complex with oxidizing agents, dichalcogenides, and a thiophosphinic amide have been studied. Treatment of the reported homoleptic DMAB complex [Ce(DMAB)₃] (<b>1</b>) with Ag(OTs) (OTs^- = tosylate) and Ag(OTf) (OTf^- = triflate) in tetrahydrofuran (thf) afforded [Ce₄(DMAB)₆(μ-OTs)₆(thf)₂] (<b>2</b>) and [Ce(DMAB)₂(OTf)(thf)₂] (<b>3</b>), respectively. Reactions of <b>1</b> with CuI and CuCl led to isolation of [Ce(DMAB)₂I] (<b>4</b>) and [Cu₄(DMAB)₄], respectively. Treatment of <b>1</b> with PhEEPh (E = S, Se) and tetramethylthiuram disulfide ([Me₂NC(S)S]₂) in thf afforded [Ce₂(DMAB)₂(EPh)(μ-EPh)₃(thf)₂] (E = S (<b>5a</b>), Se (<b>5b</b>)) and [Ce{S₂CNMe₂}₃(thf)₂], respectively. In the presence of 1,3,4,6,7,8-hexahydro-2<i>H</i>pyrimido[1,2-<i>a</i>]pyrimidine (hppH), the reaction of <b>1</b> with 2,2'-dipyridyl disulfide ([PyS]₂) yielded [Ce₂(PyS)₄(μ-hpp)₂] (<b>6</b>). Protonolysis of <b>1</b> with a bis(thiophosphinic amido)amine ligand, H₂L, afforded [Ce(L)(DMAB)(thf)] (<b>7</b>) that reacted with Ag(OTf) to give [Ce(L)(OTf)(thf)₂] (<b>8</b>). Migratory insertion of <b>7</b> with <i>N</i>,<i>N</i>'-dicyclohexylcarbodiimide and phenyl isothiocyanate resulted in the formation of an amidine (<b>9</b>) and a thioacetamido (<b>10</b>) complex, respectively. The crystal structures of the Ce-DMAB complexes have been determined.