Inorganic Chemistry Communications (v.8, #4)

Contents List (iii-iv).

Fortuitous formation of [(LiCl)6{(Me2NCH2C8H5N)3P}2]: an amine-ligated hexameric lithium chloride aggregate by Mark R. Mason; Floyd A. Beckford; Kristin Kirschbaum; Bradford J. Gorecki (331-334).
Deprotonation of gramine with n BuLi and subsequent reaction with PCl3 yielded a novel hexameric lithium chloride aggregate ligated by six dimethylamino groups from the intended product, tris{(3-dimethylaminomethyl)indolyl}phosphine. The preparation and spectroscopic and structural characterization of the title complex are reported.Deprotonation of gramine with n BuLi and subsequent reaction with PCl3 yielded [(LiCl)6{(Me2NCH2C8H5N)3P}2] (2). Compound 2 was characterized by NMR (1H, 13C, 31P) spectroscopy, elemental analysis, and X-ray crystallography. The molecular structure of 2 reveals a novel hexameric lithium chloride aggregate ligated on each of two hexagonal faces by three dimethylamino groups from the intended product, tris{(3-dimethylamino-methyl)indolyl}phosphine. Crystal data for 2  · 3CH2Cl2: C36H45Cl9Li3N6P, monoclinic, P21/n, a  = 12.732(4) Å, b  = 22.251(6) Å, c  = 16.815(5) Å, β  = 108.233(5)°, V  = 4525(2) Å3, Z  = 4, D calc  = 1.369 g/cm3.
Keywords: Lithium chloride; Aggregates; Phosphines; Gramine;

A copper(II) chain compound with hydrogenphosphate bridges organized in a double-chain structure. Synthesis, structure and magnetic properties of [Cu(1,10-phenanthroline)(μ-HPO4)(H2O)2] n by Sujittra Youngme; Pongthipun Phuengphai; Chaveng Pakawatchai; Gerard A. van Albada; Stefania Tanase; Ilpo Mutikainen; Urho Turpeinen; Jan Reedijk (335-338).
A new Cu(II) chain compound, [Cu(1,10-phenanthroline)(μ-HPO4)(H2O)2] n 1 has been synthesized hydrothermally and structurally characterized. The Cu(II) ion is tetragonally coordinated with a phen ligand and two aqua ligands in the equatorial plane and hydrogenphosphates as axial ligands, thereby forming a linear chain. The crystal lattice is formed from antiparallel chains, kept together by relatively strong phosphate–water H-bonds (intra- and intermolecular) and by interpenetrated stacking of the phen ligands with other chains. The magnetic susceptibilities are reported.A new Cu(II) chain compound, [Cu(1,10-phenanthroline)(μ-HPO4)(H2O)2] n 1 has been synthesized hydrothermally and structurally characterized by elemental analysis, IR, EPR spectrum and single-crystal X-ray diffraction. The Cu(II) ion is tetragonally coordinated with a phen ligand and two aqua ligands in the equatorial plane (Cu–N distance 2.006(2) Å and Cu–O distance 1.969(2) Å) and hydrogenphosphates as axial ligands (Cu–O distance 2.470(2) Å), thereby forming a linear chain. The crystal lattice is formed from antiparallel chains, kept together by relatively strong phosphate–water H-bonds (intra- and intermolecular) with O⋯O contacts of 2.615(3) and 2.672(3) Å and by interpenetrated stacking of the phen ligands with other chains. The magnetic susceptibility measurements (5–300 K) agrees with a weak antiferromagnetic chain interaction between the Cu centers with J value of −5.86 cm−1.
Keywords: Hydrothermal synthesis; Copper(II); Polymeric; One-dimensional chain; Magnetic properties;

The interaction of nickelocene with 3,6-di-tert-butyl-o-benzoquinone by A.V. Piskunov; G.K. Fukin; Yu.A. Kurskii; V.K. Cherkasov; G.A. Abakumov (339-342).
The interaction of nickelocene with 3,6-di-tert-butyl-o-benzoquinone in toluene gives new 18-electron (η5-Cp)Ni(η3-cyclopentenyl type ligand) complex as the main product of hetero-Diels–Alder reaction. This process being carried out in THF solution is accompanied by ligands exchange and leads mainly to strong paramagnetic complex bis(3,6-di-tert-butyl-o-benzosemiquinonate)-bis(tetrahydrofuran)nickel(II).The interaction of nickelocene with 3,6-di-tert-butyl-o-benzoquinone in toluene gives new 18-electron complex (η5-cyclopentadienyl)(η3-{5,8-di-tert-butyl-3a,9a-dihydro-1H-cyclopenta(b)[1,4]benzodioxin-1-il})nickel(II) as the main product of hetero-Diels–Alder reaction. This process being carried out in THF solution is accompanied by ligands exchange and leads mainly to octahedral complex bis(3,6-di-tert-butyl-o-benzosemiquinonate)-bis(tetrahydrofuran)nickel(II).
Keywords: Nickelocene; o-Quinone; π-Allyl complex; o-Semiquinone; X-ray diffraction;

A new magnesium porphyrazinate with eight [triphenyl-(2-sulfanyl-ethoxycarbonyl-2-propyl)phosphonium]bromide groups has been prepared from octakis(2-hydroxyethylthio)porphyrazinatomagnesium and (2-carboxy-1-methylethyl)triphenylphosphonium bromide {[(Ph)3PCH2CH(Me)CO2H]Br}. The new compound has been characterized by FT-IR, UV–Vis, 1H and 31P NMR together with elemental analysis.A new magnesium porphyrazinate with eight [triphenyl-(2-sulfanyl-ethoxycarbonyl-2-propyl)phosphonium]bromide groups has been prepared from octakis(2-hydroxyethylthio)porphyrazinatomagnesium and (2-carboxy-1-methylethyl)triphenylphosphonium bromide {[(Ph)3PCH2CH(Me)CO2H]Br}. The new compound has been characterized by FT-IR, UV–Vis, 1H and 31P NMR together with elemental analysis.
Keywords: Phthalocyanine; Porphyrazine; Triphenylphosphine; Phosphonium;

Syntheses, characterization and photochemical properties of new NO–ruthenium(II) complexes by Marı́lia Gama Sauaia; Fabiana de Souza Oliveira; Renata Galvão de Lima; Angélica de Lima Cacciari; Elia Tfouni; Roberto Santana da Silva (347-349).
The synthesis, chemical and photochemical properties of cis-[RuII(bpy)2L(NO0)](PF6)2 (L = pyridine, 4-picoline or 4-acetylpyridine) in physiological solution are reported. The photolysis of cis-[RuII(bpy)2(4-pic)(NO0)]2+ with light of 532 nm forms cis-[RuII(bpy)2(4-pic)(H2O)]2+ and nitric oxide.The synthesis, chemical and photochemical properties of cis-[RuII(bpy)2L(NO0)](PF6)2 (L = pyridine, 4-picoline or 4-acetylpyridine) in physiological solution are reported. The photolysis in the visible region of cis-[RuII(bpy)2(4-pic)(NO0)]2+ produces nitric oxide and cis-[RuII(bpy)2(4-pic)(H2O)]2+, suggesting the possibility to use such nitrosyl ruthenium complexes photochemically in therapy.
Keywords: Nitric oxide; Ruthenium complexes; Nitrosyl ruthenium complexes;

A novel heterospin system [MnIII(3-OMesalophen)(H2O)2]2[MnIII(3-OMesalophen)(H2O)] [WV(CN)8] · 2H2O consists of Mn 6 III W 2 V distinguishable structural and magnetic units due to the presence of cyano-bridged anionic MnIIIWV dimers and bis-μ-aqua-bridged dimers of [Mn(3-OMesalophen)(H2O)2]+ cations linked by H-bonds and π–π stacking interactions; it exhibits the strong antiferromagnetic coupling through the single cyano bridge and significant AF couplings through the hydrogen bonds.The synthesis, X-ray structure and magnetic properties of a new octacyanotungstate(V) based zero-dimensional [MnIII(3-OMesalophen)(H2O)2]2[MnIII(3-OMesalophen)(H2O)] [WV(CN)8] · 2H2O (1) system are reported. Compound 1 crystallizes in the triclinic system, has space group P 1 ¯ and unit cell dimensions a  = 13.494(2) Å, b  = 17.080(4) Å, c  = 18.739(5) Å with Z  = 2. The structure of 1 consists of the dimeric Mn–NC–W cyano-bridged {[Mn(3-OMesalophen)(H2O)][W(CN)8]}2− anions and bis-μ-aqua-bridged dimers of [Mn(3-OMesalophen)(H2O)2]+ cations linked by H-bonds and π–π stacking into Mn 6 III W 2 V distinguishable structural and magnetic units. The magnetic behavior of 1 correspond to a dominant antiferromagnetic coupling within the cyano-bridged {MnIIIWV}2− dimer (J 1  = −20 cm−1) and weaker AF coupling between hydrogen bonded moieties (J 2  = −0.46 cm−1) with zero-field splitting D parameter of Mn(III) centre in axially distorted surroundings of −4.0 cm−1.
Keywords: Octacyanotungstate; Manganese(III) complex; Cyano bridge; Magnetic properties; Crystal engineering;

One step synthesis of a new asymmetric water-soluble phosphine by Mireia Condom; Joan Suades (355-357).
The new asymmetric water-soluble cationic phosphine (S)-(−)-(3-diphenylphosphino-2-hydroxypropyl)trimethylammonium was synthesised from the accessible and inexpensive (S)-(−)-(3-chloro-2-hydroxypropyl)trimethylammonium chloride by means of a one pot reaction with sodium diphenylphosphide in liquid ammonia. The palladium complex (L)PdCl3 was prepared and characterised by spectroscopic methods.The new asymmetric water-soluble phosphine (S)-(−)-(3-diphenylphosphino-2-hydroxypropyl)trimethylammonium chloride was synthesised from the accessible (S)-(−)-(3-chloro-2-hydroxypropyl)trimethylammonium chloride by means of a one pot reaction between this ionic compound and sodium diphenylphosphide in liquid ammonia. The palladium complex (L)PdCl3 (L = (S)-(−)-(3-diphenylphosphino-2-hydroxypropyl)trimethylammonium) was prepared by reaction between this ligand and PdCl2(PhCN)2 and was characterised by spectroscopic methods.
Keywords: Phosphine; Asymmetric; Water-soluble; Pd(II) complex;

A series of reactions with selenocystamine and its analogous disulfide molecule were carried out in aqueous solutions. It was observed that diselenide was faster reactive to gold(III) compare to its analogous disulfide molecule. The results are compared with similar diselenide and disulfide molecule with other gold(I) drugs. In this paper, we have demonstrated that Au(III) selectively reacts first with diselenide and after complete reactions of diselenide the excess Au(III) reacts with disulfide. This observation is very significant from gold-based drug point of view.Gold(III) reacts with selenocystamine (diselenide) and immediately breaks the diselenide-bond as observed by 13C NMR spectroscopy. It is also observed that diselenide is more reactive to gold(III) compare to its analogous disulfide (cystamine) molecule. The results are compared with similar diselenide and disulfide molecule with other gold(I) drugs.
Keywords: Gold(III); Selenocystamine; Oxidation;

The synthesis, crystal structure, fluorescent and thermal properties of the Cd(II) coordination polymer [Cd(1,4-BDOA)(1,10-phen)] · H2O are reported. Each Cd(II) atom has N2O5 pentagonal bipyramidal geometry, and connected by the 1,4-BDOA2− ligands to form two-dimensional layer network. It possesses strong blue fluorescent emission in the solid state.Hydrothermal reaction of Cd(NO3)2  · 4H2O with 1,10-phen and 1,4-BDOAH2 yields a two-dimensional cadmium(II) coordination polymer, [Cd(1,4-BDOA)(1,10-phen)] · H2O, in which CdN2O5 pentagonal bipyramids are linked together to construct a lamellar structure. It exhibits strong blue fluorescent upon photoexcitation.
Keywords: Cd(II) Carboxylate coordination polymer; Benzene-1,4-dioxyacetic acid; Hydrothermal synthesis; Fluorescent property;

The binuclear metal complexes with deprotonated 1-benzyl-1,4-dihydronicotinamide as a bridging ligand were produced by the reaction of 1-benzylnicotinamidium cation coordinating to a Ru(II) or Re(I) complex with a metal hydrido complex.Ruthenium(II) and rhenium(I) complexes with a deprotonated 1-benzylamidium cation as ligand are reduced by metal hydrido complexes. The products are binuclear complexes with a deprotonated 1-benzyl-1,4-dihydronicotinamide (BNAH) ligand, such as [{Ru(tpy)(bpy)}2(BNAH-H+)]3+. The reducing ability of [{Ru(tpy)(bpy)}2(BNAH-H+)]3+ is similar to that of free BNAH but less than for the corresponding mononuclear [Ru(tpy)(bpy)(BNAH-H+)]+.
Keywords: Binuclear complex; NAD(P) model compound; Hydrido complex;

Novel tumor chemotherapeutic agents and tumor radio-imaging agents: Potential tumor pharmaceuticals of ternary copper(II) complexes by Ming-Zhao Wang; Zhao-Xing Meng; Bo-Li Liu; Guan-Liang Cai; Chun-Li Zhang; Xiang-Yun Wang (368-371).
Potential tumor chemotherapeutic agents and tumor radio-imaging agents of – Cu2+–salicylidene–amino acid Schiff bases–Phen (Bipy) ternary complexes have been designed and synthesized, their antitumor activity and tumor imaging of 64Cu labeled ones have been tested in tumor-bearing mice.Potential tumor chemotherapeutic agents and tumor radio-imaging agents of – Cu2+–salicylidene–amino acid Schiff bases–Phen (Bipy) ternary complexes have been designed and synthesized, their antitumor activity and tumor imaging of 64Cu labeled ones have been tested in tumor-bearing mice.
Keywords: Copper(II); Salicylidene–amino acid Schiff base; Phen (Bipy); Antitumor activity; Tumor radio-image;

Aminopeptidase function of dinuclear zinc(II) complexes with chiral dinucleating ligands: Stereoselectivity by chiral substrate recognition by Hiroshi Sakiyama; Kazuhide Ono; Tetsuya Suzuki; Katsuya Tone; Tomoko Ueno; Yuzo Nishida (372-374).
The aminopeptidase functions of chiral dinuclear zinc(II) complexes [Zn2(R-bppmp)(MeCO2)2]BPh4 (1R) and [Zn2(S-bppmp)(MeCO2)2]BPh4 (1S) were estimated using l-leucine-p-nitroanilide as a substrate [H(R/S-bppmp): 2,6-bis[{(R/S)-1-phenylethyl-2-pyridylmethyl}aminomethyl]-4-methylphenol].Both complexes showed aminopeptidase activity, and the activity for 1S was 2.3 times greater than that for 1R.The aminopeptidase functions of newly obtained chiral dinuclear zinc(II) complexes [Zn2(R-bppmp)(MeCO2)2]BPh4 (1R) and [Zn2(S-bppmp)(MeCO2)2]BPh4 (1S) were estimated using l-leucine-p-nitroanilide as a substrate [H(R/S-bppmp): 2,6-bis[{(R/S)-1-phenylethyl-2-pyridylmethyl}aminomethyl]-4-methylphenol]. Both complexes showed aminopeptidase activity, and a second-order rate equation was obtained as v  =  k [complex][substrate]. The rate constants k were 3.3(7) × 10−2 for 1R, and 7.6(5) × 10−2 dm3  mol−1  s−1 for 1S in a mixture of 40% DMF and 60% aqueous solution at pH 8.0, and the activity for 1S was 2.3 times greater than that for 1R. Molecular mechanics calculation indicated that 1S is very suitable for substrate incorporation.
Keywords: Dinuclear zinc(II) complexes; Chiral dinucleating ligand; Aminopeptidase function; Stereoselectivity;

Hydrothermal reactions of zinc(II) acetate, 2,2′-bipyridine (bipy), TeO2 and NH4VO3 at 170 °C lead to a novel organically covalent-bonded zinc(II) vanadium(V) tellurite, Zn2(bipy)2V4TeO14 (1). The structure of 1 features a new type of layered structure built from 1D double chains of Zn(bipy)V3O9 interconnected by 1D chains of Zn(bipy)VTeO6 via V–O–Te bridges.Hydrothermal reactions of zinc(II) acetate, 2,2′-bipyridine (bipy), TeO2 and NH4VO3 at 170 °C lead to a novel organically covalent-bonded zinc(II) vanadium(V) tellurite, Zn2(bipy)2V4TeO14 (1). The structure of 1 features a new type of layered structure built from 1D double chains of Zn(bipy)V3O9 interconnected by 1D chains of Zn(bipy)VTeO6 via V–O–Te bridges.
Keywords: Zn–V tellurite; Hydrothermal reaction; Layered materials; Crystal structure;

A novel 3D coordination complex [Cd(H2L) · 1.5H2O] n with strong yellow emission was obtained by self-assembly between a amido-containing multidentate ligand N,N′-bis(4-pyridylcarboxyl)-2,6-pyridine dicarbohydrazide (H4L) and cadmium(II).A novel three-dimensional cadmium(II) coordination complex [Cd(H2L) · 1.5H2O] n with space group P6(2) was obtained by self-assembly between H4L and cadmium(II). Each cadmium ion is seven coordinated by four nitrogen and three oxygen atoms from the H2L2−, forming a coordination geometry of distorted pentagonal bipyramid. This complex exhibits intense yellow emission at room temperature.
Keywords: Cadmium complex; Three-dimensional network; Crystal structure; Fluorescence;

Design of single cyanide-bridged tetranuclear bimetallic rectangles exhibiting ferromagnetic coupling by Luminita Marilena Toma; Rodrigue Lescouëzec; Danielle Cangussu; Rosa Llusar; José Mata; SharonSpey; Jim A. Thomas; Francesc Lloret; Miguel Julve (382-385).
The cyanide-bridged tetranuclear bimetallic rectangles ( XPh 4 ) 4 [ Fe 2 III Cu 2 II ( μ - CN ) 4 ( CN ) 8 ( L ) 2 ] · n H 2 O [X = P (1) and As (2); L = bpcam (1) and bpca (2); n  = 4 (1) and 0 (2)] have been prepared and characterized by X-ray diffraction; 1 exhibits intramolecular ferromagnetic interactions leading to a low-lying quintet spin state.The cyanide-bridged tetranuclear bimetallic rectangles ( XPh 4 ) 4 [ Fe 2 III Cu 2 II ( μ - CN ) 4 ( CN ) 8 ( L ) 2 ] · n H 2 O [X = P (1) and As (2); L = bpcam (1) and bpca (2); n  = 4 (1) and 0 (2)] have been prepared and their crystal structures were characterized by single crystal X-ray diffraction; 1 exhibits intramolecular ferromagnetic interactions (J 1  = +3.7 cm−1 and J 2  = +7.0 cm−1, H = - J 1 [ S Fe ( 1 ) · S Cu ( 1 ) + S Fe ( 1 a ) · S Cu ( 1 a ) ] − J 2 [ S Fe ( 1 ) · S Cu ( 1 a ) + S Fe ( 1 a ) · S Cu ( 1 ) ] + D [ S Fe ( 1 ) z 2 + S Fe ( 1 a ) z 2 ] ) leading to a low-lying S  = 2 spin state.
Keywords: Iron; Copper; Cyanide; Magnetic properties; Ferromagnetic coupling; Tetranuclear rectangles;

A new ferrocene functionalized receptor was synthesized and characterized. The electrochemical responses of the receptor in the absence and presence of cations and anions have been determined using cyclic voltammetry technique at different pH values. The electrochemical studies reveal that the receptor can be used as a sensor for Cu(II) ion as well as for fluoride ion.A new pH responsive ferrocene functionalized receptor N,N′-bis(3-ferrocenylmethyl aminopropyl)oxamide (R) was synthesized and characterized. The electrochemical responses of the receptor R as a function of pH have been determined using cyclic voltammetric technique. Increase in H+ ion concentration in the medium increases the redox potential of the Fc/Fc+ redox couple of the receptor. Addition of metal ions like Mn(II), Ni(II) and Zn(II) show anodic shift of the Fc/Fc+ redox couple. The presence of Cu(II) ion shows cathodic shift of the Fc/Fc+ redox couple at acidic pH values. The potential shifts between the free receptor and the receptor with anions (F, Cl and Br) at different pH were determined. Among the halide anions, fluoride ion shows appreciable amount of cathodic potential shift.
Keywords: Chemosensor; Ferrocene; Cationic sensor; Anionic sensor; Electrochemical studies;

A eutectic mixture of choline chloride/urea is liquid at ambient temperature and is used as a non-volatile reaction medium for the synthesis and crystallization of a novel coordination polymer, [Zn(O3PCH2CO2)] · NH4, in which structure-directing ammonium ions are generated in situ from the partial decomposition of urea.A eutectic mixture of choline chloride/urea is liquid at ambient temperature and is used as a non-volatile reaction medium for the synthesis and crystallization of a novel coordination polymer, Zn(O3PCH2CO2) · NH4, in which structure-directing ammonium ions are generated in situ from the partial decomposition of urea.
Keywords: Eutectic mixture; Molten salts; Coordination polymer; Phosphonate;

2-Pyridinyl-4-pyridinylmethanone functions as a bridging ligand in forming linear coordination polymers with metal(II) salts.The reaction of 2-pyridinyl-4-pyridinylmethanone with Zn(II), Co(II) and Cd(II) salts gives rise to different linear coordination polymers each linked into a three-dimensional network by intermolecular hydrogen-bonding between the aqua ligands, with additional π–π stacking interactions in the case of the Co(II) and Cd(II) complexes.
Keywords: Bridging ligand; Coordination polymer; Hydrogen bonding; Pyridyl ketone;

By reaction of (NH4)2[MoCl5(H2O)] with KNCO in hot pyridine, a mixture of mononuclear complexes containing mer-[Mo(NCO)3py3] and trans-[Mo(NCO)4py2] species (py = pyridine) has been obtained. After the separation, the crystals of two complexes, mer-[Mo(NCO)3py3] · 2py and trans-(py2H)[Mo(NCO)4py2], have been prepared. The structures of both Mo(III) complexes were confirmed by X-ray analysis.By refluxing of a mixture of (NH4)2[MoCl5(H2O)] and KOCN in pyridine, the neutral mer-[Mo(NCO)3py3] and anionic trans-[Mo(NCO)4py2] species originated simultaneously at reflux temperature. After a separation of the water-unsoluble neutral and water-soluble ionic species, the single crystals of compounds [Mo(NCO)3py3] · 2py (1) and (py2H)[Mo(NCO)4py2] (2) have been prepared and crystal structures of both were determined by X-ray crystallography.
Keywords: Molybdenum(III); Isocyanate; Pyridine; Crystal structure;

Two Cd supramolecular complexes are obtained from diffusion method and characterized by X-ray crystallography, fluorescence spectroscopy and IR spectra. In both compounds, the Cd2+ atoms are linked by sip3− into a one-dimensional zig zag chain. The zigzag chains are further linked together by hydrogen bonds and π–π stacking interactions to form supramolecular open frameworks.The reaction of Cd(NO3)2 with 5-sulfoisophthalic acid monosodium salt (NaH2sip) in the presence of piperazine (pip) or ethylenediamine (en) produced three-dimensional supramolecular complexes [Cd(sip)(Hpip)(H2O)2] (1) and [Cd(sip)(H2O)3] · 0.5(H2en) · H2O (2). In both compounds, the Cd2+ atoms are linked by sip3− into a one-dimensional zig zag chain. The resultant negative ribbons are charge balanced by the coordinated protonated pip (Hpip) in 1 but by free, half occupied H2en in 2. The zigzag chains are further linked together by hydrogen bonds and π–π stacking interactions to form supramolecular open frameworks. Both 1 and 2 show violet–blue photoluminescence at room temperature.
Keywords: Supramolecular complexes; Cadmium complexes; Crystal structures; Photoluminescence;

The control of helicity at the supramolecular level is a fascinating challenge for chemists. This paper provides a short mini-review of recent advances in the design and construction of helical coordination polymers that are categorized based on designing different types of bridging ligands. Chiral coordination polymers based on helical topologies built from chiral or achiral bridging ligands and their potential applications are also presented.The control of helicity at the supramolecular level is a fascinating challenge for chemists. This paper provides a short mini-review of recent advances in the design and construction of helical coordination polymers that are categorized based on designing different types of bridging ligands. Chiral coordination polymers based on helical topologies built from chiral or achiral bridging ligands and their potential applications are also presented.
Keywords: Helix; Chirality; Coordination polymer; Self-assembly; Supramolecular chemistry; Crystal engineering;