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標題: Preparation and characterization of cobalt-containing P,N-ligands and an unusual palladium complex ion pair: their applications in amination reactions
作者: Hsiao, Y.C.
Chiang, W.Y.
Weng, C.M.
Hong, F.E.
關鍵字: bidentate ligand;palladium complex;cobalt complex;dppm;cross-coupling reactions;cationic rhodium complexes;suzuki-miyaura;molecular-structure;phosphine ligand;selective hydrogenation;binuclear complexes;organic-synthesis;crystal-structure;aryl;chlorides
Project: Tetrahedron
期刊/報告no:: Tetrahedron, Volume 64, Issue 40, Page(s) 9507-9514.
Several cobalt-containing P,N-ligands, alkyne-bridged dicobalt phosphines [(mu-PPh(2)CH(2)PPh(2))CO(2)(CO)(4)(mu,eta-Me(2)NCH(2)C CPR(2))] (4a: R=(t)Bu; 4b: R=Ph; 4c: R=Cy), were prepared from the reactions of corresponding alkynylphosphines Me(2)NCH(2)C CPR(2) (2a: R=(t)Bu; 2b: R=Ph; 2c: R=Cy) with a dppm-bridged dicobalt complex [CO(2)(CO)(6)(mu-P,P-PPh(2)CH(2)PPh(2))] 3. A unique palladium complex ion pair [(mu-PPh(2)CH(2)PPh(2))CO(2)(CO)(4)(mu,eta-Me(2)NCH(2)C=CP ((t)Bu)(2))Pd(eta(3)-C(3)H(5))(+)[(eta(3)-C(3)H(5))PdCl(2)](-) 7a was obtained from the reaction of 4a with [(eta 3-C(3)H(5))PdCl](2). Compounds 4a, 4b, and 4c are authentic cobalt-containing P,N-bidentate ligands and can be used for ligation of palladium from various Sources such as Pd(OAc)(2) or [(eta(3)-C(3)H(5))PdCl](2). Satisfactory efficiencies were observed for the amination reactions of aryl bromides with morpholine employing either a 4a-chelated palladium complex formed in situ or pre-formed 7a as the catalytic precursor. (C) 2008 Elsevier Ltd. All rights reserved.
ISSN: 0040-4020
DOI: 10.1016/j.tet.2008.07.076
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