Tai Hasegawa

The crystal structures of α, ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-Aromatic molecule inclusion compounds. V. Toluidine clathrates of the hosts built of the diamines, 1,4-diaminobutane, 1.5-diaminonentane, and 1,8-diaminooctane

The crystal structures have been analyzed for the threeo-toluidine clathrates,catena-[catena-μ-(1,4-diaminobutane)cadmium(II) tetra-μ-cyanonickelate(II)]-o-toluidine(2/3),4-o,catena-[catena-μ-(1,5-diaminopentane)cadmium(II) tetra-μ-cyanonickelate(II)]-o-toluidine(3/4),5-o, andcatena-[catena-μ-(1,8-diaminooctane)cadium(II) tetra-μ-cyanonickelate(II)]-o-toluidine(1/1),8-o, for am-toluidine onecatena-[catena-μ-(1,5-diaminopentane)cadmium(II) tetra-μ-cyano-nickelate(II)]-m-toluidine(1/1),5-m, and for ap-toluidine onecatena-[catena-μ-(1,8-diaminooctane)cadium(II) tetra-μ-cyanonickelate(II)]-p-toluidine(1/1),8-p. 4-o crystallizes in the triclinic space groupPī,a/Å = 9.806(3),b/Å = 14.388(3),c/Å = 7.725(2), α/° = 89.71(2), β/° = 89.96(2), γ/° = 98.12(2),V/Å3 = 1078.8(5),Z = 2, 3750 reflections,R = 0.056;5-o: tetragonalP4lmmm, (a = b)/Å = 7.485(7),c/Å = 10.06(3),V/Å3 = 563(2),Z = 1, 573 reflections,R = 0.19;8-o: monoclinicP2/m,a/Å = 11.513(4),b/Å = 7.626(1),c/Å = 7.101(1), β/° = 109.63(3),V/Å3 = 587.2(2),Z = 1, 1682 reflections,R = 0.058;5-m: orthorhombicPbam,a/Å = 12.254(6),b/Å = 20.62(1),c/Å = 7.804(1),V/Å3 = 1972(1),Z = 4, 2240 reflections,R = 0.059; and8-p: triclinic,Pī,a/Å = 11.52(1),b/Å = 7.632(3),c/Å = 7.039(4), α/° = 88.93(4), β/° = 109.71(5), γ/° = 82.81(9),V/Å3 = 576.9(6),Z = 1, 2598 reflections,R = 0.042. Their structures are substantially similar to the already-known structure ofcatena-[catena-μ-(1,6-diaminohexane)cadmium(II) tetra-μ-cyanonickelate(II)]-o-toluidine(1/1): the guest toluidine molecules are accommodated in the cavities formed betweencatena-[cadmium(II) tetra-μ-cyanonickelate(II)] layers bridged by the ambidentate α,ω-diaminoalkane ligands at the cadmium(II) atoms. The carbon chain length of the α,ω-diaminoalkane influences the number of cavities per formula unit and the deformation of the metal complex layers.

The twisted skeleton of 1,9-diaminononane incatena-[catena-,μ-(1,9-diaminononane)cadmium(II) tetra-μ -cyanonickelate(II)]-o-xylene(2/1)

The Hofmann-danon-typeo-xylene clathrate Cd[NH2(CH2)9NH2]Ni(CN)4·0.5(CH3)2C6H4, crystallizes in the triclinic space groupPĪ witha = 15.118(3),b = 14.048(4),c = 7.325(1) Å, α = 91.50(2), β = 131.66(3), and γ = 107.50(2)°,V = 1051(1) Å3 andZ = 2. The structure, refined toR = 0.047 using 2851 reflections, reveals a three-dimensional host framework built of the layers of a two-dimensionalcatena-[cadmium tetra-μ-cyanonickelate(Il)] network and of the ambidentate 1,9-diaminononane (danon) bridging the Cd atoms in adjacent networks. The guesto-xylene molecule is accommodated in the cavity formed in the interlayer space similar to that in the Hofmann-daotn-type. The skeleton of the danon in the Cd-NC9N-Cd linkage takes a (gauche)2(trans)8 conformation twisted at the (gauche)2 part in contrast with the all-trans conformation of 1,8-diaminononane in the Hofmann-daotn-type clathrate. The twisted (gauche)2 part of the danon skeleton occupies the interlayer space to such an extent that void space available for the guest o-xylene molecule decreases to half that in the Hofmann-daotn-type clathrate Cd[NH2(CH2)8NH2]Ni(CN)4·G.

2-Mercaptobenzoxazole pentacyanoferrate(II/III) complexes: UV-Visible, Mössbauer, electron paramagnetic resonance, electrochemistry and molecular modeling

2-Mercaptobenzoxazole pentacyanoferrate(II/III) complexes, [FeII/III(CN)5(bzoxs)]3-/2- , were prepared in MeOH/H2O 75:25% solutions and characterized by spectroscopic UV-Vis, Mossbauer, electron paramagnetic resonance (epr) and electrochemical-cyclic voltammetry- techniques. UV-Vis and epr spectra along with the electrochemical behavior suggested the coordination of the multi-functional N,S,O- donor ligand, bzoxs, to iron(III) through the sulfur atom. The crystal field parameters, DqL and Dt, calculated for the iron(II) complex, in addition to the reversible redox process FeIII-bzoxs + e- ® FeII-bzoxs also pointed to coordination via the sulfur atom. The results were compared with the chemical properties of pentacyanoferrate complexes containing other monodentate N-, S- and O-donor ligands. Ab initio calculations revealed the composition of the frontier orbitals of bzoxs and are in agreement with the mode of coordination proposed from the experimental data.

The first water soluble metal-enediyne complexes: structural characterization of trans-[Os(en)2(η2-L)Br]+Br− (en = ethylenediamine, L = cis-1,6-bistrimethylsilyl-3-ene-1,5-diyne)

Abstract The first water soluble metal-enediyne complexes have been prepared by displacement of the dihydrogen ligand of [Os(II)(en)2(η2-H2)(H2O)](OTf)2 (en = ethylenediamine, OTf = CF3SO3−), 1, with an enediyne molecule, cis-1,6-bistrimethylsilyl-3-ene-1,5-diyne, 2. Different σ donor ligands can be introduced to the trans position of the enediyne ligand to prepare different metal-enediyne complexes. The single crystal X-ray analysis of trans-[Os(en)2(η2-L)Br]+Br− (L = cis-1,6-bistrimethylsilyl-3-ene-1,5-diyne), 4, shows that the osmium(II)(en)2 moiety binds specifically to the double bond of the enediyne molecule. This structure represents a new mode of metal-enediyne coordination. 4 crystallizes in the monoclinic space group P2 1 /a, with Z = 4, a = 13.150(2) A , b = 11.38(4) A , c = 18.413(9) A , and β = 100.74(2)° . The structure was solved by direct methods and refined to conventional agreement indices R = 0.054 and Rw = 0.048 with 2880 unique reflections for which 1 > 3 σ(1).

A new capped iron(III) trinuclear benzoate cluster

The new cluster [Fe3O(C7H5O2)6(phen)(H2O)]NO3 was prepared and characterized by atomic absorption, elemental analysis, mass spectrometry, Mössbauer, IR, UV-vis and EPR spectroscopies. Structural information was obtained from quantum mechanics calculations using the molecular mechanics (MM+) approach. This cluster has only one labile coordination site suitable for ligand substitution and can be used as a starting material to the rational assemble of polynuclear compounds.

NEW LIPOPHILIC BISPOCKET-PORPHYRINS FOR CHEMOTHERAPY OF CANCER (PART I); PREPARATION AND PROPERTIES OF 5,10,15,20-TETRAKIS(3′,5′-DI-t-BUTYLPHENYL) PORPHYRIN METAL COMPLEXES1

Abstract A series of highly lipophilic bis-pocket porphyrins, 5,10,15,20-tetrakis(3′, 5′-di-t-butylphenyl)porphyrin with five metals (copper(II), nickel(II), zinc(II), cobalt(II), and iron(III)), have been prepared and characterized on the basis of electronic, infrared and 1H NMR spectra. Although electronic spectra of these porphyrins are substantially the same as their prototype tetraphenylporphyrin complexes of the respective metals, their solubility in common organic solvents such as chloroform, benzene, and hexane is dramatically enhanced.

SYNTHESES OF CYANOMETAL INCLUSION COMPOUNDS (PART I): PREPARATION AND CHARACTERIZATION OF catena-[catena-(α,ω‐DIAMINOHEXANE)CADMIUM-μ‐TETRACYANONICKELATE]‐χGEST COMPLEXES

Abstract Synthetic details of a series of clathrate compounds of general formula, catena-[catena-(α,ω‐diaminohexane)cadmium-μ-tetracyanonickelate]‐χGuest, are described. The coefficient χ, i.e. the number of guest molecules per unit of the host metal complex, is estimated for each complex. The features of this type clathrate are discussed.