Alkylation-Induced O-Atom Rearrangement in Nickel S-Oxygenates

Autor:	Marcetta Y. Darensbourg, Rizalia M. Buonomo, Joseph H. Reibenspies, Craig A. Grapperhaus, John A. Bellefeuille
Rok vydání:	1998
Předmět:	Organic Chemistry chemistry.chemical_element Halide Sulfoxide Crystal structure Alkylation Electrochemistry Ring (chemistry) Medicinal chemistry Inorganic Chemistry Nickel chemistry.chemical_compound chemistry Nucleophile Physical and Theoretical Chemistry
Zdroj:	Organometallics. 17:5212-5212
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om980857t
Popis:	Reactions of organic halides MeI and Br(CH2)3Br with square planar nickel complexes of tetradentate N2SS‘ or N2S‘2 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−SO2R) and metallothiolates (Ni−SR) (which were subsequently alkylated to nickel-bound thioethers). Proposed intermediates in the reactions of the monosulfoxide, Ni-4*, N-(2-mercapto-2-(methylpropyl))-N‘-(2-sulfenato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) and the bis-sulfoxide, Ni-5*, N,N‘-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 N-(sulf...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::6668a100ec5055ee6e7eada25c92f792 https://doi.org/10.1021/om980857t Zobrazit plný text záznamu