3 years ago

Palladium(II) complexes of homologated ferrocene phosphanylether and thioether ligands

Ales Machara, Ivana Cisarova, Petr Stepnicka, Martin Zabransky
The reaction of [1'-(diphenylphosphanyl)ferrocenyl]methanol-borane (1/1) with in situ formed N,N,N',N',S-pentamethylisothiouronium iodide and sodium hydride, followed by removal of the borane protecting group with 1,4-diazabicyclo[2.2.2]octane afforded 1'-(diphenylphosphanyl)-1-[(methylthio)methyl]ferrocene (3) as a new, homologated, hybrid phosphanylferrocene ligand. Compound 3 and the congeneric phosphanyl-ether 2 were studied as ligands in Pd(II) complexes. When reacted with [PdCl2(cod)] at the 1:1 Pd-to-ligand ratio, compound 3 produced a mixture of two Pd complexes, including the ligand-bridged dimer [(m(P,S)-3)PdCl2]2 (6), which was structurally characterized. Upon increasing the ligand amount to 2 equiv., the similar reaction produced the bis-phosphane complex [PdCl2(3-kP)2] (7). Bridge-cleavage reactions of the dipalladium complex [(LNC)Pd(m-Cl)]2 (LNC = 2-[(dimethylamino-κN)methyl]phenyl-κC1) with donors 3 and 2 proceeded in a uniform manner to give the corresponding phosphane complexes [(LNC)PdCl(3-kP)] (8) and [(LNC)PdCl(2-kP)] (9). Conversely, removing the Pd-bound chloride from these complexes with AgClO4 generated the bis-chelate complex [(LNC)Pd(3-k2P,S)] (10) and the aqua complex [(LNC)Pd(H2O)(2-kP)] (11), which could be both converted back to their precursors by adding Bu4NCl. The structures of the complexes 6-11 (some in a solvated form) were determined by single-crystal X-ray diffraction analysis.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201701057

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