Inorganic Chemistry Communications (v.4, #8)

Contents (iii-iv).

Synthesis and characterization of a novel tetranuclear nickel(II) complex: [Ni4(μ-OH)2(μ-dppn)4(μ-H2O)2](Cl)(ClO4)5·9H2O (dppn=3,6-bis(2-pyridyl)pyridazine) by Nack-Do Sung; Ki-Seob Yun; Tae-Young Kim; Ki-Young Choi; Mancheol Suh; Jin-Gyu Kim; Il-Hwan Suh; Jik Chin (377-380).
A novel tetranuclear compound [Ni4(μ-OH)2(μ-dppn)4(μ-H2O)2](Cl)(ClO4)5·9H2O (1) (dppn = 3,6-bis(2-pyridyl)pyridazine) has been synthesized for the first time and structurally characterized. The pair of nickel atoms that are connected by the (μ-dppn) ligand are joined through the hydroxy group and water molecule bridges to form the tetranuclear core. Within this tetranuclear unit, one nickel atom is six-coordinate with distorted octahedral geometry and an N4O2 donor set from two equivalent dppn ligands and two oxygens of the bridging hydroxy and water molecule. Electronic spectra and magnetic moment of the complex also reveal a high-spin octahedral geometry.
Keywords: Crystal structure; 3,6-bis(2-pyridyl)pyridazine; Tetranuclear nickel(II) complex; Octahedral nickel(II) complex;

Homobinuclear [{Pd(dppp)}2(μ-biim)](OTf)2 (4) (dppp=bis(diphenylphosphino)propane, biim=2,2-biimidazole, OTf=OSO2CF3) is accessible by the reaction of [Pd(dppp)](OTf)2 (1) with H2biim (2) in the presence of an appropriate base. The structure of 4 was determined by X-ray crystallography. As a result thereof, the palladium atoms are located somewhat above and below the planar biim2− entity.
Keywords: Binuclear complexes; Palladium; 2,2-Biimdazole; X-ray structure;

The hydrothermal reaction of cadmium hydroxide with 4-sulfobenzoic acid and 2,2-bipyridine yields 1D coordination polymer [Cd2(L)2(2,2-bipy)2(H2O)2] n 1 (where L = 4-sulfobenzoic acid), with blue fluorescent emission in which each [Cd2(L)2(2,2-bipy)2(H2O)2] unit (an approximate rectangular molecular box) is linked together by μ3 carboxylate to result in the formation of 1D chain coordination polymer. Crystal data for 1: triclinic, space group P-1(No.2), a=8.8350(16), b=9.4770(16), c=11.8019(15)  A ̊ ; α=99.174(11), β=105.776(13), γ=113.718(15)°; V=829.1(2)  A ̊ 3 ; Z=2; R 1=0.0206, wR 2=0.0526 for 2925 independent reflections with I>2σ(I).
Keywords: Cadmium; One-dimensional coordination polymer; 4-Sulfobenzoate; Hydrothermal synthesis;

Hydrolytic DNA cleavage promoted by a dinuclear iron(III) complex by Ademir Neves; Hernán Terenzi; Rosmari Horner; Adolfo Horn Jr.; Bruno Szpoganicz; Juliet Sugai (388-391).
The dinuclear iron complex [Fe2 III(BPClNOL)2(H2O)2](ClO4)2 (1) [N–(2-hydroxybenzyl)–N–(pyridylmethyl)[(3-chloro)(2-hydroxy)]propylamine] was investigated focusing on its hydrolytic activity towards phosphate esters and DNA. The activity was evaluated within the pH range 6.1–8.0 when the hydroxo molecules are coordinated to the FeIII centers of (1). The complex did not show hydrolytic activity on the 4-nitrophenyl phosphate and bis(2,4-dinitrophenyl)phosphate. However, the complex successfully promoted the hydrolytic cleavage of plasmid DNA, producing single and double DNA strand breaks.
Keywords: DNA cleavage; Dinuclear iron(III) complex; Artificial nuclease; Drug–DNA interaction;

The syntheses of a series of zirconium Schiff-base complexes are reported. These complexes are synthesized by the reaction of zirconium (IV) isopropoxide with the unusual kind of Schiff-base in 1:1 molar ratio, and they are characterized by EA, IR and MS. When activated by excess methylaluminoxane (MAO), all complexes are active for the polymerization of ethylene.
Keywords: Zirconium; Schiff-base; Methylaluminoxane; Polymerization of ethylene;

A range of mononuclear η2-olefin complexes of ruthenium, Ru(CO)42-olefin), are prepared photochemically and their relative stabilities assessed and discussed.

Protonation, complexation and thermochemical behaviour of N-benzoylthiocarbamic-O-alkylester anions in solution by Bernd Schröder; Uwe Schröder; Frank Dietze; Lothar Beyer (398-401).
Enthalpies of protonation and metal complex formation of anions of a series of five N-benzoylthiocarbamic-O-alkylesters (R=Et, i-Pr, n-Bu, n-Hex, n-Dodec; 1–5) have been measured by titration calorimetry. Using known stability constants the reaction entropies have been calculated. The free ligands HL are verified to react as NH-acids. The remarkable gain of entropy mainly depends on the high number of lost molecules from the extended solvation shell of the reacting species in the 1,4-dioxane/water mixture. The nickel(II) cations are bound in the complex through similar forces than the NH-proton in the ligand.
Keywords: N-Benzoylthiocarbamic-O-alkylesters; Nickel(II) complexes; Titration calorimetry, pH Potentiometry;

Preparation of bis(hydrazine) complexes of iron(II) by G. Albertin; S. Antoniutti; E. Bordignon; F. Chimisso (402-404).
Bis(hydrazine) complexes [Fe(RNHNH 2)2{PPh(OEt)2}4](BPh 4)2  (R=H,CH 3) 1, 2 were prepared by allowing nitrile complexes [Fe(CH3CN)2{PPh(OEt)2}4](BPh4)2 to react with hydrazine at 0°C. The monohydrazine [Fe(NH2NH2)(CH3CN)2{P(OEt)3}3] (BPh4)2 derivative was also obtained. Treatment of bis(hydrazine) 1, 2 with Pb(OAc)4 led to the acetate complex [Fe(κ2-O2CCH3){PPh(OEt)2}4]BPh4.
Keywords: Iron; Hydrazine; Bis(hydrazine); Oxidation;

The first isonicotinato N-oxido (N-inicO) ligand bridging cadmium three-dimensional network coordination polymer, [Cd(N-inicO)2]·(H 2 O)2   1 , was synthesized using the precursor of N-inicO ligand, 1-oxide-4-cyanopyridine under hydrothermal conditions. The oxygen atom of N-oxido in N-inicO adopts a bidentate-bridging mode to connect with Cd to form a three-dimensional network with porous structure in which water molecules are included in the cavity. The bridging mode of N-inicO ligand is, to the best of our knowledge, unprecedented in the known any metal complexes containing the N-inicO ligand.
Keywords: Cadmium; Isonicotinato N-oxido; Crystal structure; Three-dimensional porous structure;

Six new chiral lanthanide complexes derived from sodium D-camphor-β-sulfonate and aminothiourea with Ln=La3+,Pr3+,Nd3+,Sm3+,Eu3+ and Gd3+ of the type LnL3 have been synthesized and characterized on the bases of their elemental analysis, molar conductance, IR, XPS, CD, electronic spectra, magnetic moments and thermal analysis methods. It was found that NaL acts as an SNO tridentate ligand. The visible spectra of PrIII and SmIII show characteristic f–f transitions and the nephelauxetic parameter (β), the bonding parameter (b 1/2) and covalency parameter (δ) of these transitions has been evaluated. These data indicate the weak involvement of the 4f orbitals in complex formation. A nine-coordinated model has been proposed for these complexes.
Keywords: Chiral complexes; Schiff base; Aminothiourea; Sodium D-camphor-β-sulfonate;

DFT calculation and X-ray structure of nitrosyl pentaammine chromium complex by Takashi Shibahara; Haruo Akashi; Masahiro Asano; Kan Wakamatsu; Kichisuke Nishimoto; Masayasu Mori (413-415).
The optimized structures of nitrosyl pentaammine chromium complex [Cr(NO)(NH3)5]2+ (A) at three different spin multiplicities, doublet (A2), quartet (A4), and sextet (A6), were obtained by ab initio calculation at B3LYP/6-31G (6-31+G for NO) level of theory. The complex A was most stable at the lowest spin multiplicity (doublet), which is in harmony with the previous magnetic measurement (μ eff=1.8 BM) of the perchlorate of A, [Cr(NO)(NH3)5](ClO4)2 ( A ). The X-ray structure of A was determined: Cr–N(NO), 1.677(6) Å; N–O, 1.180(7) Å; Cr–N(NH3,trans), 2.140(5) Å; Cr–N(NH3,cis), 2.080(6)–2.096(6) Å; Cr–N–O, 179.9(6)°. The optimized structure (A2) is in good agreement with the experimental one. The present result shows that the covalent type π bondings between Cr and N(NO), which is ascribed to the overlapping between two π orbitals of NO and two π orbitals of Cr, cause the extra stabilization of A2.
Keywords: Nitrosyl chromium complex; Density functional theory; Spin multiplicity; X-ray structure;

A novel complex of sandwich layers having disordered symbiotic distribution of azido group and water molecules by Wen-Zhen Wang; Xin Liu; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan; Xin-Kan Yao; Geng-Lin Wang (416-418).
A novel complex [Ru(bpy)3]N3Cl·2H2O was characterized by single-crystal X-ray diffraction. The complex exhibits a sandwich-type layer structure, which consists of mutually stacking layers of cations and anions. The anion layer consists of random occupied azide anions, water molecules and chloride atoms.
Keywords: Crystal structure; Sandwich-type layer structure; Ruthenium(II) complex; Random occupied anions;

A new cyanato-bridged polymeric complex [Cd3(NCO)6(NH2CH2C5H4N)3] n with a zig–zag ladder shaped structure by Chirantan Roy Choudhury; Subrata Kumar Dey; Nijhuma Mondal; Samiran Mitra; S. Ozra Ghodsi Mahalli; K.M. Abdul Malik (419-422).
A new cyanato-bridged polymeric complex [Cd3(NCO)6(NH2CH2C5H4N)3] n has been synthesized and characterized by X-ray crystallography. There are three cadmium atoms, three chelated 2-(aminomethyl)pyridine and six end-on bridging cyanato groups in the asymmetric unit. Each Cd atom is bonded to one chelated C5H4NCH2NH2 base and four μ2-NCO groups in a distorted octahedral environment. Three such independent CdN6 octahedra share their bridging edges to produce a zig–zag ladder shaped polymeric network extending along a.
Keywords: Crystal structure; Polymeric complex; Cadmium complex; Cyanato bridge;

New polymeric structure of rhenium octahedral chalcocyanide complex: Ln3+-derived network with one-dimensional channels by Sofia B Artemkina; Nikolai G Naumov; Alexander V Virovets; Sergey A Gromilov; Dieter Fenske; Vladimir E Fedorov (423-426).
A novel cyanobridged coordination polymeric complex with octahedral rhenium cyanocluster anion [Re63−Se)8(CN)6]4− and Nd3+ cation has been synthesised and structurally characterised. Its solid-state structure contains a channel-type polymeric network built from cluster anions and Nd3+ through ReCNNdNCRe interactions. For compound (H3O){Nd(DMF)3(H2O)3}[Re6Se8(CN)6], space group R3c, unit cell parameters are: a=32.514(5); c=25.255(5) Å, V=23122(7) Å3, R f=0.0762. A pair of isomorphic complexes has been obtained with Ln=Pr3+,Ho3+.
Keywords: Rhenium; Octahedral cluster; Lanthanide; Cyano-bridged complexes; Polymeric structure;

Synthesis and crystal structure of a novel compound constructed from tris-(2,2-bipy)ruthenium(II) and decatungstate by Zhengbo Han; Enbo Wang; Guoyou Luan; Yangguang Li; Changwen Hu; Peng Wang; Ninghai Hu; Hengqing Jia (427-429).
Self-assembly of tris-[2,2-bipyridine]ruthenium(II) chloride with decatungstate produced a novel cation radical salt, [Ru(bpy)3]2[W10O32]·3DMSO. This is the first product of 2,2-bipyridineruthenium(II)-polyoxometalates species. Crystal data: Monoclinic, P21/c, a=12.902(3)  A ̊ , b=21.487(3)  A ̊ , c=15.854(5)  A ̊ , β=93.46(2)°, V=4387(2)  A ̊ 3 , Z=2, R 1=0.0599, wR2=0.1183. X-ray crystallographic study showed that the crystal structure was constructed by electrostatic attraction and C–H⋯O hydrogen bonds between tris-[2,2-bipyridine]ruthenium(II) and decatungstate polyanion. The tris-[2,2-bipyridine]ruthenium molecules occupy cavities in the polyoxometalate lattice ordered along b-axis.
Keywords: Tris-(2,2-bipy)ruthenium(II); Decatungstate; Synthesis; Crystal structure;

Preparation, characterization, and X-ray crystal structure of a one-dimensional calcium-based coordination polymer with strong blue fluorescent emission by Rong-Xin Yuan; Ren-Gen Xiong; Zhen-Feng Chen; Xiao-Zeng You; Shie-Ming. Peng; G.-H. Lee (430-433).
The hydrothermal reaction of 4-cyanobenzoic acid with Ca(ClO4)2·6H2O yields the one-dimensional calcium-based coordination polymer [Ca(L)2(H2O)2] n 1 (where L= 4-cyanobenzoic acid) with strong blue fluorescent emission, and its solid-state structure has been characterized by X-ray single-crystal diffraction studies. Crystal data for 1: monoclinic, space group P2/n, a=7.154 (2), b=16.402 (3), c=7.549 (2) Å; β=115.83 (2)°; Z=2; R=0.0536 for 1410 independent reflections with I>2α(I).
Keywords: Calcium complex; Crystal structure; Hydrothermal synthesis; Blue fluorescent emission;

A novel metalloenediyne coordination polymer: serpentine structure of [Cu(OAc)4(daed)] n by Tilak Chandra; John C. Huffman; Jeffrey M. Zaleski (434-436).
The preparation and structure of a unique coordination polymer containing Cu2(OAc)4 units bridged by 1,8-bis(dimethylamino)oct-4-ene-2,6-diyne (daed) ligands is described. The structure exhibits an intriguing extended lattice that weaves to the edge of the crystal.

First examples of methylene insertion into the phosphorus(III)–nitrogen bond by Srinivasan Priya; Maravanji S. Balakrishna; Joel T. Mague (437-440).
The reaction of N-substituted phosphinous amides with paraformaldehyde leads to methylene insertion into the P–N bond, followed by the oxidation of phosphorus from P(III) to P(V) state. The product, Ph2P(O)CH2NHPh was characterised by a single-crystal X-ray diffraction study. The reaction not only depends on the acidic proton on the nitrogen, but also on the oxidation state of phosphorus and it is considered to proceed through Staudinger–Wittig pathway.
Keywords: Insertion; Phosphinoamine; Phosphine oxide; Paraformaldehyde;

A nickel(II) complex with 2-hydroxy-N,N -bis(1-methyl-3-hydroxy-3-phenyl-2-propen-1-ylidene)-1,3-propanediamine (H3L),[Ni4(L)2(CH3O)2(CH3OH)2], was synthesized and structurally characterized. The X-ray crystal structure shows that the compound has a tetranuclear structure with a mixed-spin state consisting of octahedral NO5 and planar NO3 coordination environments, which is formed by alkoxo-bridges. Magnetic susceptibility data show ferromagnetic behavior.
Keywords: Nickel complex; Tetranuclear complex; Schiff-base; Magnetic property;

Synthesis and structures of two novel heterometallic polymers by C.-P. Cui; P. Lin; W.-X. Du; L.-M. Wu; Z.-Y. Fu; J.-C. Dai; S.-M. Hu; X.-T. Wu (444-446).
The cyanide act as a bridging ligand between metal atoms and it usually gives to polymeric compound with 2D or 3D networks, two novel heterometallic polymers containing CN ligands {[Et4N]2[WS4Cu4(CN)2Br2]} n (1) and [ZnCu4(CN6(dmf)4] n (2) have been synthesized and characterized in this paper.
Keywords: Heterometallic polymers; Cyanide; Bridging ligand; Crystal structure;

Synthesis and crystal structure of 1,2-bis(phthalimidomethyl)-1,2-dicarba-closo-dodecaborane(12): a precursor to polyamines by Yinghuai Zhu; Hongming Zhang; John A. Maguire; Narayan S. Hosmane (447-449).
The reaction of 1 equivalent of the dilithium salt of the [closo-1,2-C2B10H10]2− dianion with two equivalents of N-(bromomethyl)phthalimide, in a mixture of anhydrous benzene and diethyl ether, produced a new bis-C(cage)-substituted o-carborane, 1,2-bis(phthalimidomethyl)-1,2-dicarba-closo-dodecaborane(12) (1) in 65% yield.
Keywords: Phthalimidomethyl; bis-Substituted; Dicarbadodecaborane; Polyamine; BNCT;