Alkylation-Induced O-Atom Rearrangement in Nickel S-Oxygenates BellefeuilleJohn A. GrapperhausCraig A. BuonomoRizalia M. ReibenspiesJoseph H. DarensbourgMarcetta Y. 1998 Reactions of organic halides MeI and Br(CH<sub>2</sub>)<sub>3</sub>Br with square planar nickel complexes of tetradentate N<sub>2</sub>SS‘ or N<sub>2</sub>S‘<sub>2</sub> ligands (S‘ = RS(O)) have been explored for their potential to direct alkylation of metallosulfoxide sulfur and yield metal-bound organic sulfoxides. In fact, as established by spectroscopic and electrochemical signatures, isolated products were characterized as the result of O-atom rearrangements or transfers leading primarily to metallosulfones (Ni−SO<sub>2</sub>R) and metallothiolates (Ni−SR) (which were subsequently alkylated to nickel-bound thioethers). Proposed intermediates in the reactions of the monosulfoxide, <b>Ni-4*</b>, <i>N</i>-(2-mercapto-2-(methylpropyl))-<i>N</i>‘-(2-sulfenato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) and the bis-sulfoxide, <b>Ni-5*</b>, <i>N</i>,<i>N</i>‘-bis(2-sulfenato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II), with 1,3-dibromopropane include S-bound R‘S−OR moieties resulting from ring closure of the pendant alkyl bromide on the nucleophilic sulfoxide oxygen. X-ray crystal structures of <i>N</i>-(sulfinato-2-(methylpropyl))-<i>N</i>‘-(2-thia-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) iodide and a bimetallic composed of two units of <i>N</i>-(2-mercapto-2-(methylpropyl))-<i>N</i>‘-(2-sulfinato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) linked by (CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>) are reported.