Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes.

Armitt, David J.; Bruce, Michael I.; Gaudio, Maryka; Zaitseva, Natasha N.; Skelton, Brian W.; White, Allan H.; Le Guennic, Boris; Halet, Jean-François; Fox, Mark A.; Roberts, Rachel L.; Hartl, František; Low, Paul J.

Abstract

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiC[triple bond, length as m-dash]CC6F5 and RuCl(dppe)Cp′ [Cp′ = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C[triple bond, length as m-dash]CC6F5)(dppe)Cp′ [Cp′ = Cp (2); Cp* (3)], which are related to the known compound Ru(C[triple bond, length as m-dash]CC6F5)(PPh3)2Cp (1). Treatment of Me3SiC[triple bond, length as m-dash]CC6F5 with Pt2(μ-dppm)2Cl2 in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt2(μ-dppm)2(C[triple bond, length as m-dash]CC6F5)2 (4). The Pd(0)/Cu(I)-catalysed reactions between Au(C[triple bond, length as m-dash]CC6F5)(PPh3) and Mo(≡CBr)(CO)2Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co3(μ3-CBr)(μ-dppm)(CO)7 or IC[triple bond, length as m-dash]CFc [Fc = (η5-C5H4)FeCp] afford Mo(≡CC[triple bond, length as m-dash]CC6F5)(CO)2Tp* (5), Co3(μ3-CC[triple bond, length as m-dash]CC6F5)(μ-dppm)(CO)7 (6) and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC6F5 (7), respectively. The diruthenium complexes 1,4-{Cp′(PP)RuC[triple bond, length as m-dash]C}2C6F4 [(PP)Cp′ = (PPh3)2Cp (8); (dppe)Cp (9); (dppe)Cp* (10)] are prepared from 1,4-(Me3SiC[triple bond, length as m-dash]C)2C6F4 in a manner similar to that described for the monoruthenium complexes 1–3. The non-fluorinated complexes 1,4-{Cp′(PP)RuC[triple bond, length as m-dash]C}2C6H4 [(PP)Cp′ = (PPh3)2Cp (11); (dppe)Cp (12); (dppe)Cp* (13)], prepared for comparison, are obtained from 1,4-(Me3SiC[triple bond, length as m-dash]C)2C6H4. Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes 2–3 and 8–13, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes 1, 2, 3, 6 and 10.

Citation

Armitt, D. J., Bruce, M. I., Gaudio, M., Zaitseva, N. N., Skelton, B. W., White, A. H., Le Guennic, B., Halet, J.-F., Fox, M. A., Roberts, R. L., Hartl, F., & Low, P. J. (2008). Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes. Dalton Transactions, 2008(47), 6763-6775. https://doi.org/10.1039/b808798a

• Journal Article Type: Article
• Acceptance Date: Aug 21, 2008
• Online Publication Date: Oct 17, 2008
• Publication Date: Dec 21, 2008
• Deposit Date: Dec 14, 2011
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 2008
• Issue: 47
• Pages: 6763-6775
• DOI: https://doi.org/10.1039/b808798a
• Public URL: https://durham-repository.worktribe.com/output/1502232