Issue 45, 2015
From the journal:

Chemical Communications

Rapid Markovnikov addition of HCl to a pendant alkyne: evidence for a quinoidal cumulene†

Samantha G. Eaves,ab   Sam J. Hart,c   Adrian C. Whitwood,c   Dmitry S. Yufit,a   Paul J. Low*b  and  Jason M. Lynam*c  

* Corresponding authors

a Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK

b School of Chemistry and Biochemistry, Bayliss Building, The University of Western Australia, 35 Stirling Highway, Crawley, Perth, Western Australia 6009, Australia
E-mail: paul.low@uwa.edu.au
Tel: +61 8 6488 3045

c Department of Chemistry, University of York, Heslington, York, UK
E-mail: jason.lynam@york.ac.uk
Tel: +44 (0)1904322534

Abstract

Reaction of cis-[RuCl2(dppm)2]BF4 with TlBF4 and 1,4-diethynyl-benzenes results in the formation of the vinylidene cations trans-[Ru([double bond, length as m-dash]C[double bond, length as m-dash]CH–C6H2-2,5-R2-4-C[triple bond, length as m-dash]CH)Cl(dppm)2]+ (R = H, Me). Subsequent reaction with [NnBu4]Cl results in nucleophilic attack at the coordinated organic ligand, but not at the expected metal-bound carbon atom. Instead, trans-[Ru(C[triple bond, length as m-dash]C–C6H2-2,5-R2-4-CCl[double bond, length as m-dash]CH2)Cl(dppm)2] was generated which, when coupled with DFT calculations, provides evidence for an intermediate quinoidal cumulene complex.

Graphical abstract: Rapid Markovnikov addition of HCl to a pendant alkyne: evidence for a quinoidal cumulene

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Article information

DOI
https://doi.org/10.1039/C4CC09696G
Article type
Communication
Submitted
04 Dec 2014
Accepted
22 Dec 2014
First published
22 Dec 2014

Chem. Commun., 2015,51, 9362-9365

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Rapid Markovnikov addition of HCl to a pendant alkyne: evidence for a quinoidal cumulene

S. G. Eaves, S. J. Hart, A. C. Whitwood, D. S. Yufit, P. J. Low and J. M. Lynam, Chem. Commun., 2015, 51, 9362 DOI: 10.1039/C4CC09696G

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