Mitsuru Kondo

Synthesis, structure, and magnetic properties of one-dimensional copper(II) coordination polymer, [Cu(pyrazine-2,3-dicarboxylate)(H2O)2]·2H2On

Abstract A title compound has been synthesized and characterized. The complex crystallizes in the monoclinic space group C 2/ c with a = 12.768(1) A, b = 7.5159(8) A, c = 13.271(1) A, β = 123.591(4) °, V = 1060.8(2) A 3 and Z = 4. The complex consists of onedimensional chains of copper(II) ions bridged by pyrazine-2,3-dicarboxylate. Each copper ion has a distorted octahedral coordination with N 2 O 4 chromophor. The magnetic susceptibility data over a range of 2–300 K were fitted by using an Heisenberg antiferromagnet, H =2 J Σ S i · S i+1 the parameters of J = −1.40 cm −1 , g = 2.14 and ρ = 0.032.

Crystal structures of optically active diastereomeric telluronium and selenonium salts anion—cation interactions in the crystalline state

Abstract The tellurium atom in optically pure diastereomeric ( R )-ethylmethylphenyltelluronium ( 1S )-camphor-10-sulfonate (( R ) Te - 1 ) was found to interact with two oxygen atoms of the counter anions in the crystalline state, while that in the other diastereomeric isomer ( S ) Te - 1 interacts with three oxygen atoms. This difference in interactions is considered to be caused by steric factors (crystal packing) and not to be caused by electronic effects, since the telluronium cations have the same substituents and counter anions. The crystal packing structure of ( R ) Te - 1 showed M -helix geometry through anion—cation interactions, while that of ( S ) Te - 1 showed a 2D-sheet structure. The corresponding optically active selenonium salt ( R ) Se - 2 showed crystal packing similar to that of ( R ) Te - 1 .

OXAMIDE OXIME-BASED COPPER(II) COORDINATION POLYMERS. TWO- AND THREE-DIMENSIONAL STRUCTURES CONTROLLED BY DICARBOXYLATES

Abstract The new Cu(II) complex, [Cu(H2oao)(L(1,2))(H2O)] (1), and coordination polymers, {[Cu(H2oao) (L(2,4))]·H2O}n (2) and {[Cu(H2oao)(Hoao)]·(HL(2,2))}n (3) (H2oao = oxamide oxime; H2L(1,2) = maloic acid; H2L(2,4) = succinic acid; H2L(1,2) = maleic acid), have been synthesized and their structures have been X-ray crystallographically characterized. 1 crystallizes in the monoclinic, space group P21/c with a = 10.186(1), b = 6.648((1), c = 14.748(3) A, β = 102.06(1)°, U = 976.5(3) A 3 and Z = 4. The mononuclear units in 1, in which L(1,2)2− chelates to Cu(II) ions, are linked to form a two-dimensional sheet structure through hydrogen bonds between coordinated H2oao and L(1,2)2−. Additional hydrogen bonds link the layers to form a three-dimensional hydrogen bonding network. 2 crystallizes in the monoclinic, space group P21/n with a = 14.739(4), b = 9.994(3), c = 7.101(2) A , β = 98.52(2)°, U = 1034.4(5) A 3 and Z = 4. The Cu(II) ions in 2 are bridged by L(2,4)2− coordinated in an amphimonodentate mode, forming a one-dimensional zigzag chain. The water of crystallization is hydrogen bonded to both L(2,4)2− and H2oao of an adjacent chain, forming a two-layered sheet. Further weak hydrogen bonds link another chain, and an extended three-dimensional hydrogen bonding network runs through the crystal. 3 crystallizes in the monoclinic, space group P21/c, with a = 14.817(3), b = 13.693(4), c = 7.328(2) A , β = 101.10(2)°, U = 1459.1(7) A 3 and Z = 4. In contrast to the case of 1 and 2, the dicarboxylic acid, L(2,2)2− in 3 is not coordinated to the Cu(II) ions. The axial coordination of the oximate oxygen in an adjacent Hoao to [Cu(H2oao)(Hoao)]+ leads to the formation of a one-dimensional zigzag chain. The chains are linked by hydrogen bonds between H2oao on adjacent chains to form sheets, which are sandwiched between uncoordinated HL(2,2)− layers, resulting in a segregated double sheet structure in the crystal. The obtained structures are greatly associated with the size of the spacers, which link the carboxylate groups in the dicarboxylic acids, and hydrogen bonding interactions between the ligands.

Synthesis, Structure, and Magnetic Properties of Crystalline Coordination Polymers of Copper(II), {[Cu(CA)(H2O)2 (H2O)}n AND [Cu(CA)(MeOH)2 n (H2CA; Chloranilic Acid)

Abstract Hydrogen bonded coordination polymers, {[CU(CA)(H2O)2 (H2O)}n, [Cu(CA)(MeOH)2 n (H2CA; chloranilic acid), and related polycrystalline analogs have been structurally and magnetically characterized. 1-Dimensional (1-D) weak antiferromagnetic exchange interaction (J = -2.01 cm−1) was observed in {[Cu(CA)(H2O)2 (H2O)}n, which has a 3-dimensional hydrogen bond network in the crystal. This polycrystalline form liberates the water molecules to be [Cu(CA) n, which is known as the Heisenberg antiferromagnet. Powder X-ray diffraction and thermal data show that the framework constructed by 1-D chains are so stable that water molecules readily come out without breaking the 1-D chains. Two types of coordination polymers ([Cu(CA)(MeOH)2 n and [Cu(CA)(MeOH) n) containing axially coordinated MeOH have been prepared. [Cu(CA)(MeOH) n has strong and anomalous antiferromagnetic exchange interactions in the crystal, indicating a new phase of Cu/CA systems, such as a mixed valence state, and if so the coordinated MeOH...

Synthesis, structure, and reactivities of the Ru–Co heterobimetallic complex. Molecular structures of Cp*Ru(CO)2(μ2-CO)Co(CO)3, Cp*Ru(μ2-CO)2(μ2-dppm)Co(CO)2, Cp*Ru(CNBut)(CO)(μ2-CO)Co(CO)3, and Cp*(CO)Ru{η2:η4–μ2–C(Tol)CHC(Tol)CH}Co(CO)2 (Cp*=η5-C5Me5, dppm=Ph2PCH2PPh2, Tol=C6H4Me-4)

Abstract Treatment of Cp*Ru(CO)2Cl (Cp*=η5-C5Me5) with NaCo(CO)4 produces the metal–metal bonded heterobimetallic complex Cp*Ru(CO)2(μ2-CO)Co(CO)3 (2b). Substitution of the CO ligands by the Ph2PCH2PPh2 (dppm) leads to the isolation of Cp*Ru(μ2-CO)2(μ2-dppm)Co(CO)2 (3) whereas that by ButNC gives Cp*Ru(CO)(CNBut)(μ2-CO)Co(CO)3 (4). Stoichiometric head-to-tail dimerization of p-tolylacetylene at the bimetallic site of 2b proceeds to form the dinuclear metallacyclopentadiene complex Cp*(CO)Ru{η2:η4-μ2-C(Tol)CHC(Tol)CH}Co(CO)2 (5) in which two alkyne molecules are coupled to form a ruthenacyclopentadiene core which coordinates to the Co(CO)2 fragment. On the other hand, catalytic head-to-head coupling of methyl propiolate in the presence of 2b yields (E)-(MeO2C)CHue605CH(Cue606CCO2Me) (6). The molecular structures of 2b, 3, 4, and 5 have been determined by X-ray crystallography.

Molecular structure of π-allyl palladium(II) complex, [Pd(η3-PhCHCHCHPh) -((S,S) -chiraphos)]PF6: A novel envelope conformation of chiral C2-symmetric diphosphine

Abstract The X-ray structure analysis of [Pd( η 3 -1,3-diphenylallyl)(( S,S )-chiraphos)]PF 6 shows that the conformation of the five-membered chelate ring of chiraphos is an envelope form, and the whole complex has quasi- C s -symmetry in the crystal, while the circular dichroism spectrum of the complex suggests that the chelate ring takes the gauche conformation in solution.

Synthesis, structure and reactivities of the dinuclear μ-η1:η6-arylethynyl ruthenium complexes [Cp(PR3)2Ru(μ-η1:η6-CCC6H4Me-p)RuCp*]·Cl (R=Ph, Me; Cp=η5-C5H5, Cp*=η5-C5Me5). The molecular structure of [Cp(PPh3)2Ru(μ-η1:η6-CCC6H4Me-p)RuCp*]·PF6

Abstract Treatment of [Cp(PR3)2Ru(Cue606CC6H4Me-p) (1a, R=Ph 1b, R=Me; Cp=η5-C5H5) with [Cp*Ru(μ3·Cl)]4 (Cp*=η5-C5Me5) selectively produced the novel dinuclear μ-η1:η6- arylethynyl complex Cp(PR3)2Ru(μ-η1:η6-Cue606CC6H4Me-p)RuCp*] (2·Cl: 2a, R=Ph; 2b, R=Me). Protonation of 2·OTf (OTf=OSO2CF3) by TfOH afforded the corresponding vinylidene complex [Cp(PR3)2Ru(μ-η1:η6-Cue605CHC6H4Me-p)RuCp*]·[OTf]2 (3·[OTf]2: 3a, R=Ph; 3b, R=Me), which regenerated 2·OTf upon treatment with LiBHEt3. Reaction of 2a·Cl with I2 and subsequent anion metathesis with AgBF4 produced the iodovinylidene complex [Cp(PPh3)2Ru(μ-η1:η6-Cue605CIC6H4Me-p)RuCp*]·[BF4]2 (4·[BF4]2), whereas similar treatment of 2b·PF6 yielded the iodo/arylethynyl complex [Cp(I)(PMe3)2Ru(μ-η1:η6-Cue606CC6H4Me-p)RuCp*]·[PF6]2 (5·[PF6]2). Substitution of one of the PPh3 ligands in 2a·OTf proceeded under 1 atm of CO to form [Cp(PPh3)(CO)Ru(μ-η1:η6-Cue606CC6H4Me-p)RuCp*]·OTf (6·OTf). The molecular structure of 2a·PF6 was determined by X-ray crystallography.

An oxovanadium(IV) complex chelated by dipyridyl sulfide

The complex (di-2-pyridyl sulfide-N,N)dichlorooxovanadium(IV), [VOCl 2 (C 10 H 8 N 2 S)], was prepared by the reaction of VCl 3 and sodium 2-mercaptopyridine N-oxide in ethanol solution under an atmosphere of argon. The N atoms of the dipyridyl sulfide ligand and the two chloride ligands coordinate to the oxovanadium(IV) ion, to give a complex with square-pyramidal geometry. The dipyridyl sulfide ligand forms a folded six-membered chelate ring with a larger N−V−N bite angle than that formed by 2,2-bipyridyl

Synthesis, Structure and Magnetic Properties of a Two- Dimensional Nickel(II) Coordination Polymer, {[Ni(pzdc)(pyz)].2H2O}n (H2pzdc = pyrazine-23-dicarboxylic acid; pyz = pyrazine)

Abstract A title compound has been synthesized and characterized. The complex crystallizes in the orthorhombic space group Cmcm with a = 7.004(2) A, b = 12.748(2) A, c = 13.665(2) A, V = 1220.1(3) A3 and Z = 4. The complex consists of two-dimensional square arrays of nickel(II) ions bridged by pzdc2 and pyz ligands. Each nickel ion has a slightly distorted octahedral coordination with N4O2 chromopher. The magnetic susceptibility data over a range of 2–300 K were fitted by using an Heisenberg antiferromagnet with a mean field approximation. The obtained J and zJ values are −1.70 cm−1 and −0.70 cm−1, respectively.

Crystal structure of a binuclear vanadium(III) complex with a new tripodal ligand, [V2Cl4(tped)(EtOH)2]·2EtOH

Abstract The reaction of VCl 3 (thf) 3 (thf=tetrahydrofuran) with bis(2-pyridyl) ketone (pyke) gives a binuclear vanadium(III) complex, [V 2 Cl 4 (tped)(EtOH) 2 ]·2EtOH (tped=tetrapyridyl-1,2-ethanediol), having a new type of tripodal ligand, which comes from the reductive coupling of the pyke. This is the first dinuclear vanadium(III) complex that contains both ionic and neutral alcohol oxygen. The complex crystallizes in monoclinic space group P 2 1 / c , with a =11.420(4), b =10.978(2), c =14.826(3) A,β=103.53(2)°, V =1807.1(8) A 3 , Z =2, D calc =1.463 g cm −3 , μ(Cu Kα)=77.16 cm −1 , F (000)=820.00, R =0.040, R w =0.060, T =296(1) K for 1998 observed reflections.