Sadatoshi Akabori

Synthesis, some reactions, and molecular structure of the Pd(BF4)2 complex of 1,1′-bis(diphenylphosphino)ferrocene

Abstract 1,1′-Bis(diphenylphosphino)ferrocene (dppf) reacted with [Pd(CH 3 CN) 4 ](BF 4 ) 2 in the presence of one equivalent of phosphines to give a stable 1/1 complex in which there is a bonding interaction between Fe and Pd atoms. An X-ray structure determination of [(dppf)Pd(PPh 3 )](BF 4 ) 2 confirms the presence of a dative bond (2.877(2) A. In the case of ligands other than phosphines, no complex with a metal-metal bond was obtained.

Molecular structure and electrochemical properties of the PtII complex of 1,1′-bis(methylthio)ferrocene and the PdII complexes of 1,4,7-trithia[7]- and 1,5,9-trithia[9] (1,1′)ferrocenophanes

Abstract Molecular structures of (triphenylphosphine) [1,1′-bis-(methylthio)ferrocene-S,S′,Fe]Pt(BF4)2 (1), (1,5,9-trithia[9]ferrocenophane-S,S′,S″,Fe)Pd(BF4)2 (2), and (acetonitrile)(1,4,7-trithia[7]ferrocenophane-S,S′,S″,Fe)Pd(BF4)2 (3) were determined by X-ray analyses. The Pt in 1 and the Pd atom in 2 have a somewhat distorted square-planar geometry including the Fe atom of the ferrocene moiety, while the Pd atom in 3 is coordinated by one equivalent of acetonitrile and takes a distorted tetragonal-pyramidal geometry. The distances of the FeM bond (M = Pd, Pt) in 1–3 are 2.851(2), 2.827(2), and 3.0962(8) A, respectively. Cyclic voltammetry of 1–3 gave no reversible wave, but afforded some information supporting the presence of a dative bond.

Synthesis and some properties of Pd(BF4)2 and Pt(BF4)2 complexes of 1,1′-bis[(alkyl- or phenyl-)chalcogeno]ferrocenes

Abstract 1,1′-Bis(alkylthio and -phenylthio)ferrocenes react with (MeCN)4Pd(BF4)2 in the presence of triphenylphosphine to give stable 1/1 complexes in good yields. 1,1′-Bis(alkylseleno)ferrocenes and 1,1′-bis(phenylthio and phenylseleno)ferrocenes to give similar 1/1 complexes. Some platinum analogs were prepared from the reaction of the corresponding dichloro-complexes with AgBF4 in the presence of triphenylphosphine. The spectral data indicate that there is a dative metal-metal bond between the iron atom of the ferrocene and the palladium(II) or platinum(II) atom in these complexes.

The architecture of dinuclear Ni and Cu complexes: twisted and parallel forms controlled by the self-assembly of Schiff base ligands

Novel dinuclear complexes were synthesized through the self-assembly of macrocyclic Schiff base ligands and either nickel(II) or copper(II) ions. X-Ray structural analysis revealed that the complexes had either a double helix (twisted) structure in which each atom had a distorted square-planar coordination or a non-helical (parallel) structure in which the metals had octahedral coordination. The helical complexes were rather unusual in that their helicity originated not in the coordination centre, but mainly in the linker moieties in the ligand. Several factors influencing the formation of the helical structure are discussed.

A specific change of the electronic and 1C NMR spectra and redox potentials in 1,n-dithia[n]ferrocenophanes. A novel interaction between the sulphur atom and the ferrocene nucleus

Abstract Of the 1, n -dithia[ n ]ferrocenophanes prepared from disodium 1,1′-ferrocenedithiolate and polymethylene dibromides, the ferrocenophane with n = 7 showed the largest shift in the electronic and 13 C NMR spectra and the largest decrease of the redox potential. This can be interpreted by a new type of stereoelectronic interaction between the sulfur atom and the ferrocene nucleus.

Syntheses of ferrocenophanes containing aromatic or heteroaromatic rings in the bridging chain

Abstract 1,10-Dithia[2]- o -cyclo-, 1,10-dithia[2]- m -cyclo-, 1,10-dithia[2](2,6)pyridino-, and 1,9-dithia[2](2,5)furano-[2](1,1′)ferrocenophanes were synthesized. The structural features are discussed on the basis of spectral data and redox potentials.

Pd(BF4)2 complexes of 1,1′-bis(alkyl- or aryl-)thio]- and 1,1′-bis(diphenylphosphino)-ferrocenes. Bond formation between the Fe and Pd atoms

1,1′-Bis[(alkyl- or phenyl-)thio]- and 1,1′-bis(diphenylphosphino)-ferrocenes react with (CH3CN)4Pd(BF4)2 in the presence of triphenylphosphine to give 1/1 complexes in good yields. Spectral data have confirmed the presence of an FePd dative bond in these complexes.

Novel dimeric structure in the PdII complex of 1,10-dithia[2](2,6)pyridino[2](1,1′)ferrocenophane. A connected metal-metal interaction

Abstract The Pd(BF 4 ) 2 complex of 1,10-dithia[2](2,6)pyridino[2](1,1′)ferrocenophane was prepared. The NMR spectral data suggested that the complex has a weak dative bond between the Pd and Fe atoms. The X-ray analysis of the complex supported the suggestion and also showed that a weak PdPd bonding interaction connects two molecules, resulting in a novel dimeric structure.

Lithium ion selective dibenzo-14-crown-4 possessing a phosphoric acid functional group as a pendant

Abstract Dibenzo-14-crown-4 possessing an ionizable phosphoric acid moiety as an additional binding site of a pendant arm has been synthesized. Its complexing ability was measured by solvent extraction and transport experiment. It is disclosed that the introduction of the pendant group to the dibenzo-14-crown-4 provides a significant enhancement in the extractability and the transport rate toward only Li+ ion.

Preparation and some properties of polyoxathiaferrocenophanes

Abstract Some sulfur analogs of a crown ether-like compound containing ferrocene as a ring member were prepared. Their complexing ability was poor with alkali metal cations but good with a silver cation.