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Issue 35, 2017
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Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CH[double bond, length as m-dash]CH2 and Si–(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

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Abstract

The formation of a family of silicon- and siloxane-bridged multiferrocenyl derivatives carrying different functional groups attached to silicon, including Fc2(CH3)3C(CH2)2SiCH[double bond, length as m-dash]CH2 (5), Fc2(CH2[double bond, length as m-dash]CH–O)SiCH[double bond, length as m-dash]CH2 (6), Fc2(OH)SiCH[double bond, length as m-dash]CH2 (7), Fc2(CH2[double bond, length as m-dash]CH–O)Si–O–Si(O–CH[double bond, length as m-dash]CH2)Fc2 (8) and Fc2(CH2[double bond, length as m-dash]CH–O)Si–O–SiFc3 (9) is described. Silyl vinyl ether molecules 6, 8 and 9 and the heteroleptic vinylsilane 5 resulted from the competing metathesis reaction of lithioferrocene (FcLi), CH2[double bond, length as m-dash]CH–OLi or (CH3)3C(CH2)2Li with the corresponding multifunctional chlorosilane, Cl3SiCH[double bond, length as m-dash]CH2 or Cl3Si–O–SiCl3. The last two organolithium species have been likely formed in situ by fragmentation of the tetrahydrofuran solvent. Diferrocenylvinyloxyvinylsilane 6 is noteworthy since it represents a rare example of a redox-active silyl mononomer in which two different C[double bond, length as m-dash]C polymerisable groups are directly connected to silicon. The molecular structures of the silicon-containing multiferrocenyl species 5, 6, 8 and 9 have been investigated by single-crystal X-ray diffraction studies, demonstrating the capture and storage processes of two ring fragments resulting from the cleavage of cyclic THF in redox-active and stable crystalline organometallic compounds. From electrochemical studies we found that by changing the anion of the supporting electrolyte from [PF6] to [B(C6F5)4], the redox behaviour of tetrametallic disiloxane 8 can be switched from a poorly resolved multistep redox process to four consecutive well-separated one-electron oxidations, corresponding to the sequential oxidation of the four ferrocenyl moieties.

Graphical abstract: Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CH [[double bond, length as m-dash]] CH2 and Si–(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

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Publication details

The article was received on 23 Jun 2017, accepted on 21 Jul 2017 and first published on 24 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT02286G
Citation: Dalton Trans., 2017,46, 11584-11597
  • Open access: Creative Commons BY-NC license
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    Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CH[double bond, length as m-dash]CH2 and Si–(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

    S. Bruña, A. M. González-Vadillo, M. Ferrández, J. Perles, M. M. Montero-Campillo, O. Mó and I. Cuadrado, Dalton Trans., 2017, 46, 11584
    DOI: 10.1039/C7DT02286G

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