- A new coupling reaction for the synthesis of ruthenium half-sandwich complexes with sterically demanding cyclopentadienyl ligands
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The reaction of RuCl3(solv.)n with tert-butylacetylene in methanol or ethanol leads to the formation of chloro-bridged half-sandwich complexes with sterically demanding cyclopentadienyl ligands, which are of high interest as starting materials for the synthesis of novel Ru catalysts. The Royal Society of Chemistry.
- Gauthier, Sebastien,Solari, Euro,Dutta, Barnali,Scopelliti, Rosario,Severin, Kay
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p. 1837 - 1839
(2008/02/07)
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- Ruthenium half-sandwich complexes with sterically demanding cyclopentadienyl ligands
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A chloro-bridged RuIII complex of formula [Cp ∧RuCl2]2 (Cp∧ = η5-1-methoxy-2,4-tert-butyl-3-neopentylcyclopentadienyl) (1) was obtained in a single step by reaction of [RuCl3(solv)n] with tert-butylacetylene in methanol. Complex 1 showed polymorphism and crystallized in two distinct forms: an isomer, 1a, with no significant metal-metal interactions (Ru...Ru = 3.684(1) or 3.743(1) A) and an isomer, 1b, in which the Ru atoms are 2.960(2) A apart from each other. In solution, a temperature-dependent equilibrium between the two isomers is established. When the reaction of [RuCl3(solv)n] with tert-butylacetylene was carried out in ethanol, the chloro-bridged dimer 2, with an ethoxy instead of a methoxy group attached to the cyclopentadienyl ligand, was formed. Complex 1 was found to be a versatile starting material for the synthesis of mononuclear half-sandwich complexes. With phosphine ligands or norbornadiene (nbd), the 16 e- complexes [Cp ∧RuCl(PCy3)] (3), [Cp∧RuCl(PPh 3)] (4), and [Cp∧RuCl-(PnBu3)] (5), the 17 e- complex [Cp∧RuCl2(PPh3)] (7), and the 18 e- complexes [Cp∧RuX(PPh 2RPPh2)] (X = H, Cl; R = CH2, C 2H4; 8-11) and [Cp∧RuCl(nbd)] (12) were obtained. Crystallography analyses show that the Ru-P bond lengths in these complexes are longer than in corresponding pentamethylcyclopentadienyl complexes.
- Dutta, Barnali,Solari, Euro,Gauthier, Sebastien,Scopelliti, Rosario,Severin, Kay
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p. 4791 - 4799
(2008/10/09)
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