Palladium(II) complexes with mono-oxide 1,1 '-bis(diphenylphosphino)metallocene ligands [Fe(eta(5)-C5Me4PPh2)-(eta(5)-C5Me4P{O}Ph-2)] and [Os(eta(5)-C5H4PPh2)(eta(5)-C5H4P{O}Ph-2)]статья
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Аннотация:The monoxides [Fe(eta(5)-C5Me4PPh2)(eta(5)-C5Me4P{O}Ph-2)](1) and [Os(eta(5) -C5H4PPh2)(eta(5-)C(5)H(4)P{O}Ph-2)] (2) have been prepared by treatment of the corresponding diphosphines with CCl4 and methanol.These ligands react with [Pd(PhCN)(2)Cl-2] to give dichloride complexes of different structure.The dimeric complex [{Os(eta(5)-C5H4PPh2)(eta(5)-C5H4P{O}Ph-2)}PdCl(mu-Cl)](2) (4) contains the monodentate P-coordinated osmocene ligand with the free PjOjPh2 group, while the octamethylferrocene ligand gives the chelate k(2)-P,O complex [{Fe(eta(5)-C5Me4PPh2)(eta(5)-C5Me4P{O}Ph-2)}PdCl2] (3).The structures of 3 and 4 have been determined crystallographically.Treatment of 3 and 4 with silver salts in CH2Cl2 or acetonitrile leads to the corresponding dicationic complexes [{M(eta(5)- C5R4PPh2)(eta(5)-C5R4P{O}Ph-2)}Pd(MeCN)(x)](2+) (5, M = Fe, R = Me; 6, M = Os, R = H). Complex 5 decomposes upon isolation, in contrast 6 is rather stable, probably due to Os-Pd bonding. The dichlorides 3 and 4 catalyze catalytic amination of p-bromotoluene with N-(4-tolyl)morpholine with lower activity than (dppf)PdCl2, however they perform comparable to (dppf)PdCl2 activity in coupling of p-bromotoluene with p-methoxyphenyl boronic acid. (c) 2005 Elsevier B.V. All rights reserved.