67539-02-0Relevant articles and documents
Metal-Ligand Cooperative Proton Transfer as an Efficient Trigger for Rhodium-NHC-Pyridonato Catalyzed gem-Specific Alkyne Dimerization
Galiana-Cameo, María,Urriolabeitia, Asier,Barrenas, Eduardo,Passarelli, Vincenzo,Pérez-Torrente, Jesús J.,Di Giuseppe, Andrea,Polo, Víctor,Castarlenas, Ricardo
, p. 7553 - 7567 (2021/06/30)
The mononuclear square-planar Rh{κ2-X,N-(Xpy)}(η2-coe)(IPr) (X = O, NH, NMe, S) complexes have been synthesized from the dinuclear precursor [Rh(μ-Cl)(IPr)( η2-coe)]2 and the corresponding 2-heteroatom-pyridinate salts. The Rh-NHC-pyridinato derivatives a
Rhodium(I)-NHC Complexes Bearing Bidentate Bis-Heteroatomic Acidato Ligands as gem-Selective Catalysts for Alkyne Dimerization
Galiana-Cameo, María,Borraz, Marina,Zelenkova, Yaroslava,Passarelli, Vincenzo,Lahoz, Fernando J.,Pérez-Torrente, Jesús J.,Oro, Luis A.,Di Giuseppe, Andrea,Castarlenas, Ricardo
supporting information, p. 9598 - 9608 (2020/07/13)
A series of Rh(κ2-BHetA)(η2-coe)(IPr) complexes bearing 1,3-bis-hetereoatomic acidato ligands (BHetA) including carboxylato (O,O), thioacetato (O,S), amidato (O,N), thioamidato (N,S), and amidinato (N,N), have been prepared by reacti
Rhodium- N-Heterocyclic Carbene Catalyzed Hydroalkenylation Reactions with 2-Vinylpyridine and 2-Vinylpyrazine: Preparation of Nitrogen-Bridgehead Heterocycles
Azpíroz, Ramón,Di Giuseppe, Andrea,Passarelli, Vincenzo,Pérez-Torrente, Jesús J.,Oro, Luis A.,Castarlenas, Ricardo
, p. 1695 - 1707 (2018/06/18)
Dinuclear rhodium-NHC complexes of formula [Rh(μ-Cl)(NHC)(η2-coe)]2 react with 2-vinylpyridine to yield the chelate compounds RhCl(NHC)(κ-N,η2-CH2=CHC5H4N) {NHC = IPr, 1,3-bis(2,6-diisoprop
Pyridine-enhanced head-to-tail dimerization of terminal alkynes by a rhodium-N-heterocyclic-carbene catalyst
Rubio-Perez, Laura,Azpiroz, Ramon,Di Giuseppe, Andrea,Polo, Victor,Castarlenas, Ricardo,Perez-Torrente, Jesus J.,Oro, Luis A.
supporting information, p. 15304 - 15314 (2013/11/06)
A general regioselective rhodium-catalyzed head-to-tail dimerization of terminal alkynes is presented. The presence of a pyridine ligand (py) in a Rh-N-heterocyclic-carbene (NHC) catalytic system not only dramatically switches the chemoselectivity from alkyne cyclotrimerization to dimerization but also enhances the catalytic activity. Several intermediates have been detected in the catalytic process, including the π-alkyne-coordinated RhI species [RhCl(NHC)(η2-HC ≡CCH2Ph)(py)] (3) and [RhCl(NHC){η2-C(tBu) ≡C(E)CH=CHtBu}(py)] (4) and the RhIII-hydride-alkynyl species [RhClH{-C ≡CSi(Me) 3}(IPr)(py)2] (5). Computational DFT studies reveal an operational mechanism consisting of sequential alkyne Ci￡ H oxidative addition, alkyne insertion, and reductive elimination. A 2,1-hydrometalation of the alkyne is the more favorable pathway in accordance with a head-to-tail selectivity. Control plan: Addition of pyridine to rhodium-N-heterocyclic- carbene catalysts not only switches the chemoselectivity from alkyne cyclotrimerization to dimerization, but also enhances the catalytic activity for the formation of 1,3-enynes (see figure). A 2,1-hydrometalation of the alkyne is the more favorable pathway calculated by DFT.
SOME NEW TRANSFORMATIONS OF CYCLOPROPYLACETYLENE CATALYZED BY RHODIUM, PALLADIUM, AND COBALT COMPLEXES
Dzhemilev, U. M.,Khusnutdinov, R. I.,Shchadneva, N. A.,Nefedov, O. M.,Tolstikov, G. A.
, p. 2171 - 2174 (2007/10/02)
The linear and cyclic dimerization and trimerization of cyclopropylacetylene were carried out by the action of rhodium, palladium, and cobalt catalysts to give 2,4-dicyclopropyl-1-buten-3-yne, 1,3,6-tricyclopropylfulvene, and 1,3,5- and 1,2,4-tricycloprop
