Alkylation-induced O-atom rearrangement in nickel S-oxygenates

被引:12
作者
Bellefeuille, JA [1 ]
Grapperhaus, CA [1 ]
Buonomo, RM [1 ]
Reibenspies, JH [1 ]
Darensbourg, MY [1 ]
机构
[1] Texas A&M Univ, Dept Chem, College Stn, TX 77845 USA
关键词
D O I
10.1021/om980587e
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reactions of organic halides Mel and Br(CH2)(3)Br 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-sufenato-2-(methylpropyl))-1,5-diazacyclooc-tanenickel(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-(sulfinato-2-(methylpropyl))-N'-(2-thia-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) iodide and a bimetallic composed of two units of N-(2-mercapto-2-(methylpropyl))-N'-(2-sulfinato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) linked by (CH2CH2CH2) are reported.
引用
收藏
页码:4813 / 4821
页数:9
相关论文
共 29 条