Katsutoshi Yasufuku

Normal Vibrations of the Polymer Molecules of Helical Conformation. V. Isotactic Polypropylene and Its Deuteroderivatives

Polarized infrared spectra of isotactic polypropylene (IPP), [Complex chemical formula] were measured in the region from 4000 to 80 cm−1. The normal vibrations of these three polymers were calculated for the infrared‐ and Raman‐active A and E species, by the use of the GF‐matrix method with the Urey—Bradley force field. The results show a fairly good agreement between the observed and calculated frequencies. The assignments of the absorption bands were given, and discussions were made on the vibrational modes of the bands characteristic of the isotactic helical structures. A computation program for calculating the characteristic values and vectors of a Hermitian matrix was presented.From the normal coordinate treatment applied to the threo‐ and erythro‐ model of di‐isotactic polypropylene‐1‐d, [Complex chemical formula] it was found that the polymers prepared from trans‐ and cis‐propylene‐1‐d, CHD, CH–CH3, have threo‐ and erythro‐di‐isotactic structures, respectively, suggesting cis‐opening mechanism in t...

Chemistry of mixed transition-metal complexes : II. Preparation of mixed transition-metal μ-diphenylphosphido complexes☆

Abstract Dehydrohalogenation reactions of HPh 2 PM′(CO) n (M′ = Fe, n =4; M′ = Ni, n = 3) with several metal halide complexes in the presence of HNEt 2 were carried out and it was found that following three types of mixed transition-metal mono-μ-phosphido complexes are obtained: The stepwise formation of a metal-metal bond from the type 3 complex (III: M,M′ = Fe) to the type 1 complex (IV: M,M′ = Fe) was found.

Chemistry of mixed transition metal complexes III. Preparation and structure of new complexes of acetylenes coordinated on iron and nickel

Reactions of (tricarbonyliron)-η-carbonyl-η-(diphenylphosphido)-η-cyclo-pentadienylnickel (I) with acetylenes, C6H5CCC6H5,C6H5CCCH3,C6H5CCH, C6H5CCCO2CH3,CH3CCCO2CH3,HCCCO2CH3 and CH3OCOCCCO2CH3, have been carried out yielding new mixed transition metal monoacetylene complexes (II). Two isomers were found for complexes involving unsymmetrical acetylenes. IR, NMR and mass data are consistent with vicinal dicarbene coordination of the acetylenes to the iron and the nickel.

Chemistry of mixed transition-metal complexes : VIII. Preparations of π-cyclopentadienyl(ferrocenylcyclobutadiene)cobalt complexes and 1,1′-(o-phenylene)ferrocenes☆

Reactions of mono- and bis-(phenylethynyl)ferrocenes with π-C5H5Co(PPh3)(RCCR′) (R, R′ = Ph, CO2CH3) or π-C5H5Co(PPh3)2 at 80 ° C were examined and several ferrocenylcyclobutadienecobalt complexes were isolated. New ferrocenes bridged with o-phenylene groups were also obtained by the reaction of bis(phenylethynyl)ferrocene.

Chemistry of mixed transition-metal complexes : IV. Preparation of tertiary phosphine derivatives of carbonyl-π-cyclopentadienyliron-μ-dicarbonyl-π-cyclopentadienylnickel☆

π-Cyclopentadienyl(L)iron-μ-dicarbonyl-π-cyclopentadienylnickel (LPPh3, PPh2CH3, PPh(CH3)2, P(CH3)3 and P(OPh)3) compounds were prepared by the reaction of π-C5H5Ni(L)X with NaFe(CO)2C5H5. Insertion of SnCl2 into the metal-metal bond of the analogous complex where LCO was found to give new mixed transition metal complex, π-C5H5(CO)2FeSnCl2Ni(CO)-π-C5H5.

Chemistry of mixed transition-metal complexes : VII. Iron- and nickel-substituted cyclobutadiene complexes of cobalt☆

Abstract The preparation of π-cyclopentadienyl(substituted cyclobutadiene)cobalt complexes by the reaction of π-C5H5Co(PPh3)(RCCR′) (R, R′ = Ph, CO2CH3 with ethynyl complexes R″CCM (R″ = Ph for M = π-C5H5Fe(CO)(L);R″ = Ph, Co2CH3 for M = π-C5H5Ni(PPh3)) is described.

Molecular structure of π-C5H5NiFe(CO)3Ph3PCCH

Abstract The mixed metal complex π-C 5 H 5 NiFe(CO) 3 Ph 3 PCCH, obtained from the reaction of π-C 5 H 5 Ni(PPh 3 )CCH with Fe 2 (CO) 9 , is shown by an X-ray diffraction study to contain the ethynyltriphenylphosphonium group as the bridging ligand. Based on this structure, new reactions of [Ph 3 PCCPh]Br with some organometallic compounds have been attempted from which π-C 5 H 5 NiFe(CO) 3 (Ph 3 PC 2 Ph) and CoFe(CO) 6 (Ph 3 PC 2 Ph) can be obtained.

A facile route to (β-alkoxycarbonyl)vinylstannanes

Abstract Substituted vinylchlorostannanes of the types Cl 3 SnC(R) CHCO 2 CH 3 (R  H, CO 2 CH 3 , C 6 H 5 or CH 3 ) and Cl 3 SnCH  C(CO 2 CH 3 )SnCl 2 CH  CHCO 2 CH 3 have been prepared. On reaction with metal couples or tin the monovinyl compounds are transformed into the divinyl species Cl 2 Sn[C(R)  CHCO 2 CH 3 ] 2 . Bonding in the products is discussed in terms of their IR, 1 H NMR and 13 C NMR spectra.

Laser photolysis studies of chloro(tetraphenylporphynato)carbonylrhodium(III) in benzene solutions. Photo-induced decarbonylation and triplet formation

Abstract Laser photolysis studies of chloro(tetraphenylporphynato)carbonylrhodium(III) in benzene solutions revealed that the triplet formation, photo-induced decarbonylation, and the isomer formation occur within 20 ns after the laser pulse. Only the triplet yield was found to be dependent on the laser excitation wavelengths (532 and 355 nm).