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E/Z isomerism in monoalkylated derivatives of [Pt₂(μ-S)₂(PPh₃)₄] containing 2,4-dinitrophenylhydrazone substituents

Abstract
Alkylation of [Pt₂(m-S)₂(PPh₃)₄] with 2,4-dinitrophenylhydrazone-functionalized alkylating agents XC6H4C{¼NNHC₆H₃(NO₂)₂}CH2Br (X¼H, Ph) gives monoalkylated cations [Pt₂(m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}C₆H₄X}(PPh₃)₄]⁺. An X-ray diffraction study on [Pt₂(m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}Ph}(PPh₃)₄]BPh₄ shows the crystal to be the Z isomer, with the phenyl ring and NHC₆H₃(NO₂)₂ groups mutually trans. ¹H- and ³¹P{¹H} NMR spectroscopic methods indicate a mixture of Z (major) and E (minor) isomers in solution, which slowly convert mainly to the E isomer. Reaction of [Pt₂(m-S)₂ (PPh₃)₄] with the dinitrophenylhydrazone of chloroacetone [ClCH₂C{¼NNH(C₆H₃(NO₂)₂}Me] and NaBPh₄ gives [Pt₂ (m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}Me}(PPh₃)₄]BPh₄, which exists as a single (E) isomer.
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Journal Article
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Citation
Ujam, O.T., Devoy, S.M., Henderson, W., Wilkins, A.L. & Nicholson, B.K. (2011). E/Z isomerism in monoalkylated derivatives of [Pt₂(μ-S)₂(PPh₃)₄] containing 2,4-dinitrophenylhydrazone substituents. Journal of Coordination Chemistry, 64(16), 2782-2790.
Date
2011
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