1104876-28-9Relevant articles and documents
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-Franois,Fox, Mark A.,Roberts, Rachel L.,Hartl, Frantiek,Low, Paul J.
, p. 6763 - 6775 (2009/03/11)
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 Me3SiCCC6F5 and RuCl(dppe)Cp′ [Cp′ = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(CCC6F5)(dppe)Cp′ [Cp′ = Cp (2); Cp* (3)], which are related to the known compound Ru(CCC6F 5)(PPh3)2Cp (1). Treatment of Me 3SiCCC6F5 with Pt2(μ-dppm) 2Cl2 in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt2(μ-dppm)2(CCC6F 5)2 (4). The Pd(0)/Cu(i)-catalysed reactions between Au(CCC6F5)(PPh3) and Mo(≡CBr)(CO) 2Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co3(μ3-CBr)(μ-dppm)(CO)7 or ICCFc [Fc = (η5-C5H4)FeCp] afford Mo(≡CCCC 6F5)(CO)2Tp* (5), Co3(μ 3-CCCC6F5)(μ-dppm)(CO)7 (6) and FcCCCCC6F5 (7), respectively. The diruthenium complexes 1,4-{Cp′(PP)RuCC}2C6F4 [(PP)Cp′ = (PPh3)2Cp (8); (dppe)Cp (9); (dppe)Cp* (10)] are prepared from 1,4-(Me3SiCC)2C6F4 in a manner similar to that described for the monoruthenium complexes 1-3. The non-fluorinated complexes 1,4-{Cp′(PP)RuCC}2C6H 4 [(PP)Cp′ = (PPh3)2Cp (11); (dppe)Cp (12); (dppe)Cp* (13)], prepared for comparison, are obtained from 1,4-(Me3SiCC)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.
