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Synthesis and structure of an unusual di-rhodium diarylbutadiyne pi-complex featuring a mu-(1,2-eta(2)):(3,4-eta(2))-p-CF3C6H4-C C-C C-C6H4-p-CF3 moiety.

Ward, R.M.; Batsanov, A.S.; Howard, J.A.K.; Marder, T.B.

Authors

R.M. Ward

T.B. Marder



Abstract

Reaction of the salt [Rh(PMe3)4]Cl (1) with p-F3C–C6H4–Ctriple bond; length of mdashC–Ctriple bond; length of mdashC–C6H4-p-CF3 (2) in THF gives a mixture of two related neutral π-bound diyne complexes of [Rh(PMe3)3Cl], each having two distinct CF3 resonances of equal intensity in the in situ 19F{1H} NMR spectrum. The ratio of the two products can be varied by varying the stoichiometry of the reagents. On the basis of the spectroscopic data and literature precedent, we propose Rh(PMe3)3(Cl)((1,2-η2)-p-F3C–C6H4–Ctriple bond; length of mdashC–Ctriple bond; length of mdashC–C6H4-p-CF3) (3a) and [Rh(PMe3)3(Cl)]2(μ-(1,2-η2):(1,2-η2)-p-F3C–C6H4–Ctriple bond; length of mdashC–Ctriple bond; length of mdashC–C6H4-p-CF3) (3b) as the most likely structures of the species in solution. However, upon standing overnight, single crystals of the unusual, dinuclear complex [Rh(PMe3)3(Cl)]2(μ-(1,2-η2):(3,4-η2)-p-F3C–C6H4–Ctriple bond; length of mdashC–Ctriple bond; length of mdashC–C6H4-p-CF3) (4), an isomer of 3b, form reproducibly and in good yield as two different solvates from THF/C6D6 solution. The centrosymmetric structure of 4, obtained from single-crystal X-ray diffraction data, displays a transoid orientation of the bridging diarylbutadiyne ligand.

Citation

Ward, R., Batsanov, A., Howard, J., & Marder, T. (2006). Synthesis and structure of an unusual di-rhodium diarylbutadiyne pi-complex featuring a mu-(1,2-eta(2)):(3,4-eta(2))-p-CF3C6H4-C C-C C-C6H4-p-CF3 moiety. Inorganica Chimica Acta, 359(11), 3671-3676. https://doi.org/10.1016/j.ica.2005.12.018

Journal Article Type Article
Publication Date 2006-08
Journal Inorganica Chimica Acta
Print ISSN 0020-1693
Electronic ISSN 1873-3255
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 359
Issue 11
Pages 3671-3676
DOI https://doi.org/10.1016/j.ica.2005.12.018
Keywords Diyne, Alkyne, π-Complex, Crystal structure, Rhodium, Phosphine.
Public URL https://durham-repository.worktribe.com/output/1565246