Journal
DALTON TRANSACTIONS
Volume -, Issue 35, Pages 7071-7079Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b907124p
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Funding
- University of Karlsruhe (TH)
- Deutsche Forschungsgemeinschaft (DFG)
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[Ni-2(iPr(2)Im)(4)(COD)] 1 (iPr(2)Im = 1,3-di(isopropyl)-imidazol-2-ylidene) reacts at room temperature with the thioethers methyl para-tolyl sulfide, ethyl phenyl sulfide, benzothiophene and dibenzothiophene to afford the C-S bond cleavage products [Ni(iPr(2)Im)(2)(4-CH3-C6H4)(SMe)] 2, [Ni(iPr(2)Im)(2)(C6H5)(SEt)] 3, [Ni(iPr(2)Im)(2)(1,8-benzothiophenylato)] 4 and [Ni(iPr(2)Im)(2)(C,S-dibenzothiophenylato)] 5. In contrast to the reaction of thioethers or sulfoxides (reported earlier), no C-S bond cleavage was observed for the reaction of 1 with the sulfones bezothiophene-1,1-dioxide and methyl phenyl sulfone. In those cases the stable compounds [Ni(iPr(2)Im)(2)(eta(2)-2,3-benzothiophene-1,1-dioxide)] 6 and [Ni(iPr(2)Im)(2)(eta(2)-MeSO2C6H5)] 7 with a eta(2)-coordinated sulfone ligand have been isolated. Compound 6 has been structurally characterized. S-H bond cleavage was observed using 2-methyl-2-propanthiol to afford [Ni(iPr(2)Im)(2)(H)(StBu)] 8. The reaction of 1 with disulfides led to the dithiolato complexes [Ni(iPr(2)Im)(2)(SR)(2)] (R = tBu 9, Me 10, Ph 11) by S-S bond scission.
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