Inorganic Chemistry Communications (v.12, #1)

Contents List (iii-viii).

A new sandwich-type hybrid complex, Na8{Cu(im)4(H2O)}[Cu(im)4 {Na(H2O)2Co(im)}3(BiW9O33)2] · 11H2O (1) (im = imidazole), contains trinuclear Co2+ ions in the central belt and an antennal Cu(II)–imidazole supported complex, which firstly represents a copper(II)-complex mono-supported tungstobismuthate system with sandwiched trinuclear cobalt(II) ions.A new sandwich-type hybrid complex, Na8{Cu(im)4(H2O)}[Cu(im)4 {Na(H2O)2Co(im)}3(BiW9O33)2] · 11H2O (1) (im = imidazole), has been synthesized and structurally characterized. The polyoxoanion in 1 contains trinuclear Co2+ ions in the central belt and an antennal Cu(II)–imidazole supported complex, which firstly represents a copper(II)-complex mono-supported tungstobismuthate system containing sandwiched trinuclear cobalt(II) ions. Neighboring polyanions further connect each other by disodium ions to yield a dimeric complex. The successful synthesis of 1 opens a new approach to the combination of different kinds of transition–metal ions by virtue of lacunary Keggin-type polyoxoanions, [BiW9O33]9−, as effective linkages. The magnetic investigation for 1 indicate weak antiferromagnetic interactions for trinuclear Co(II) clusters located in the polyanions.
Keywords: Tungstobismuthate; Sandwich-type; Imidazole; Antiferromagnetic;

An enantiomeric pair of sodium(I) directed chiral Schiff base organic/inorganic frameworks have been synthesized and characterized. 1 (R,R-enantiomer) and 2 (S,S-enantiomer) exhibit mirror symmetry, and the fully fused 2D comb-like layers constituted by inorganic [Na6(H2O)12] twelve-membered rings are firstly reported.An enantiomeric pair of sodium(I) directed organic/inorganic frameworks have been obtained via the Schiff base condensation between terephthaldicarboxaldehyde and sodium salts of D- or L-phenylalanine wherein two novel two-dimensional (2D) inorganic sodium(I) separating layers composed of fully fused twelve-membered [Na6(H2O)12] comb-like rings are constituted. To the best of our knowledge, they are the first structural examples of terephthaldicarboxaldehyde-based chiral Schiff base compounds and 2D [Na x (H2O) y ] n robust inorganic frameworks.
Keywords: Chirality; Schiff base; Organic/inorganic frameworks; Structural elucidation;

A new azido-bridged Mn(II) coordination polymer, [MnL(N3)2]n (1), (L = (E)-3-(dimethylamino)-1-(pyridin-2-yl)prop-2-en-1-one), has been synthesized and structurally characterized. Complex 1 shows a 2D (6, 3) structure formed by single EE- and double EO-azido ligands alternately bridging between Mn(II) ions. The magnetic susceptibility was simulated by a model of 1D uniform chain with interchain interaction, giving J  = −5.31(3) cm−1 and zJ′  = 4.5(2) cm−1.A new azido-bridged Mn(II) coordination polymer, [MnL(N3)2]n (1) (L = (E)-3-(dimethylamino)-1-(pyridin-2-yl)prop-2-en-1-one), has been synthesized and characterized by elemental analysis, IR, single crystal X-ray diffraction and magnetic measurement. X-ray analysis shows that complex 1 is a 2D network with (6, 3) layers, in which double end-on (EO) azido-bridged dimers are linked by single end-to-end (EE) azido bridges. Magnetic susceptibilities of 1 were measured under a magnetic field of 2 KOe applied over the temperature range 300–1.8 K. The analysis of magnetic data indicates that the EO- and EE-azido bridges mediate the ferromagnetic and antiferromagnetic exchange interactions, respectively, with the antiferromagnetic coupling between Mn(II) ions dominating the magnetic properties of 1.
Keywords: Azido ligand; Coordination polymer; Magnetic property; Manganese(II) complex;

Synthesis and crystal structure of the singly tucked-in derivative of bis(phenyltetramethylcyclopentadienyl)titanium by Jiří Pinkas; Ivana Císařová; Ana Conde; Rosa Fandos; Michal Horáček; Jiří Kubišta; Karel Mach (11-14).
The X-ray diffraction data for the singly tucked-in paramagnetic titanocene [Ti(III)(η5-C5Me4Ph){η51-C5Me3Ph(CH2)}] (9) afford by nearly one order better precision of molecular parameters than those for the singly tucked-in permethyltitanocene [Ti(III)(η5-C5Me5){η51-C5Me4(CH2)}], till now the only compound of this type.Thermolysis of [TiMe25-C5Me4Ph)2] (4) at 145 °C for 5 h afforded the singly tucked-in paramagnetic titanocene [Ti(III)(η5-C5Me4Ph){η51-C5Me3Ph(CH2)}] (9). In distinction to the singly tucked-in permethyltitanocene [Ti(III)(η5-C5Me5){η51-C5Me4(CH2)}] (1) which was found crystallographically disordered [J.M. Fischer, W.E. Piers, V.G. Young, Jr., Organometallics 15 (1996) 2410] the single crystal X-ray diffraction analysis of 9 afforded molecular parameters with nearly by one order better precision as measured by esd-values.
Keywords: Titanium; Titanocene; Tucked-in; Phenyltetramethylcyclopentadienyl ligand; Thermolysis; X-ray crystallography; NMR spectra; EPR spectra;

The reaction of [W(eg)3] (eg = 1,2-ethanediolato dianion) with a phenolic ligand 2,4-di-tert-butyl-6-(((2-hydroxyethyl)(methyl)amino)methyl)phenol (H2L) yields a monomeric oxotungsten complex [WO(eg)(L)]. This complex reacts further with Me3SiCl to forma cis- and trans-isomers of corresponding dichloro complex [WOCl2(L)]. Identical dichloro complexes were also prepared by the reaction between H2L and WOCl4.The reaction between tungsten(VI) complex [W(eg)3] (eg = 1,2-ethanediolato dianion) and a phenolic ligand precursor 2,4-di-tert-butyl-6-(((2-hydroxyethyl)(methyl)amino)methyl)phenol (H2L) affords a monomeric oxotungsten complex [WO(eg)(L)]. This complex reacts further with Me3SiCl, which leads to the displacement of ethanediolato ligand from the complex unit and formation of cis- and trans-isomers of corresponding dichloro complex [WOCl2(L)]. Identical dichloro complexes were also prepared by the reaction between H2L and WOCl4. Molecular structure of [WO(eg)(L)] was verified by X-ray crystallography.
Keywords: Alkoxide complexes; Oxo complexes; Phenolate ligands; Tungsten;

The first synthesis of the solid cobalt(II)–proline complex is described; magnetic properties, DFT computations, and dioxygen scavenging experiments are presented.A solid CoII complex with l-proline as ligand was synthesized and fully characterized using spectroscopic studies, magnetic data, and DFT calculations. Dioxygen scavenging properties were investigated by UV/Vis spectroscopy and oxymetry techniques. The Co-proline system presented very interesting properties in matter of oxygen absorption capacity both in solution and incorporated in a polymer matrix.
Keywords: Cobalt; Proline; Aminoacid; Oxygen scavenger; DFT;

An iron(III) complex of a tridentate Schiff base ligand has been synthesized and characterized by elemental analyses, infrared and UV–Vis spectroscopy. The iron complex efficiently catalyzes the selective oxidation of various sulfides to sulfoxides with UHP at room temperature within short reaction times (15 min).An hydrazone Schiff base-iron(III) complex using salicylidene benzoyl hydrazine (L) as ligand has been synthesized and characterized by elemental analyses, IR, 1H and 13C NMR and UV–Vis spectroscopy. Oxidation of sulfides to sulfoxides in one-step was conducted by this complex catalyst using urea hydrogen peroxide (UHP) in mixture of CH2Cl2/CH3OH (1:1) under air at room temperature. The effect of the reaction conditions on the oxidation of methylphenylsulfide was studied by varying the amount of the catalyst, reaction temperature, reaction time and the amount of UHP. The results showed that using this system in the oxidation of sulfides, sulfoxides were obtained as the main products, together with variable amounts of sulfones (⩽9%), depending on the nature of the substrate.
Keywords: Sulfoxide; Iron complex; Schiff base; Catalytic oxidation; UHP;

A unique coordination chemistry of sodium by Tanmay Chattopadhyay; Kazi Sabnam Banu; Soubhik Chattopadhyay; Arpita Banerjee; Sandip Mondal; Eringathod Suresh; Debasis Das (26-28).
Combination of cadmium(II) iodide, hexamethylenetetramine (urotropine) (L) and (Na) y X′ (y  = 1 for X′ = azide and dicyanamide; y  = 2 for X′ = oxalate, malonate and succinate) generates a new coordination chemistry of sodium.A new coordination chemistry of sodium has been developed by complexing it with a non-chelating neutral nitrogen donor ligand hexamethylenetetramine (urotropine) in presence of cadmium(II) iodide and the new coordination compound has been characterized by X-ray single crystal structural analysis.
Keywords: Cadmium iodide; Urotropine; Sodium ion;

Synthesis and structures of the novel triple-decker complexes with 9-nickelafluorenyl ring by Piotr Buchalski; Jolanta Zbrzezna; Kinga Suwińska (29-31).
The new triple-decker compounds 2 (C32H33Ni3PF6) and 2a (C42H53Ni3PF6) were synthesised in the reaction of the oxidized 9-nickelafluorenyl sandwich complexes of Nickel (II) 1 (C27H28Ni2PF6) and 1a (C32H38Ni2PF6) in acetone. Decomposition of 1 and 1a followed by the stacking of {CpNi} species on compounds 1 and 1a resulted in the formation of the triple-decker complexes. Compound 2 was characterized by X-ray single crystal analysis. It crystallizes from dichloromethane and diethyl ether mixture in the orthorhombic crystal system and in the Pna21 space group.The new triple-decker compounds 2 (C32H33Ni3PF6) and 2a (C42H53Ni3PF6) were synthesised in the reaction of the oxidized 9-nickelafluorenyl sandwich complexes of Nickel (II) 1 (C27H28Ni2PF6) and 1a (C32H38Ni2PF6) in acetone. Decomposition of 1 and 1a followed by the stacking of {CpNi} species on the compounds 1 and 1a, respectively, resulted in the formation of the triple-decker complexes. The compound 2 was characterized by X-ray single crystal analysis. It crystallises from dichloromethane and diethyl ether mixture in the orthorhombic crystal system and the Pna21 space group.
Keywords: Nickel; Triple-decker; Clusters; Cyclopentadienyl; Metallacyclic compounds;

A new bridging ligand, 1,3-bis(4′-methyl-2,2′-bipyridin-4-yl)propan-2-one (L) and its mono- and dinuclear Ru(II) complexes have been synthesized and characterized. The carbonyl group in L keeps its character and does not affect the Ru(II) moieties. In addition, the two Ru(II) terminuses of the dinuclear complex have no interaction through the bridging linkage.A new bridging ligand, 1,3-bis(4′-methyl-2,2′-bipyridin-4-yl)propan-2-one (L) and its mono- and dinuclear Ru(II) complexes have been synthesized and characterized. The carbonyl group in L keeps its character and does not affect the Ru(II) moieties. In addition, the two Ru(II) terminuses of the dinuclear complex have no interaction through the bridging linkage.
Keywords: Mono- and dinuclear Ru(II) complexes; Carbonyl group; NMR; Spectroscopic properties; Electrochemistry;

Surprising formation of a silicon containing macrocycle by Uwe Böhme; Julia Haushälter (35-37).
The elimination of hydrogen chloride from an azomethine Schiff base during the reaction with PhSiCl3 leads to a tetracoordinate silicon complex. Surprisingly a macrocyclic product is obtained containing two ligand molecules and two PhSi-units.The reaction of a tridentate O,N,O-ligand of Schiff base type with PhSiCl3 leads surprisingly to the formation of a macrocyclic silicon–enamine derivative and not to a pentacoordinate silicon complex.
Keywords: Macrocyclic; Silicon; Siloxane; Schiff base ligand;

Synthesis, characterizations, and crystal structure of a novel layered phosphonate: Zn2Cl[O3PCH2N(CH2CH2)2O][O3PCH2NH(CH2CH2)2O] by Yan-Yu Zhu; Jing Li; Zhen-Gang Sun; Jing Zhang; Yan Zhao; Na Zhang; Lei Liu; Xin Lu (38-40).
A novel layered zinc phosphonate, Zn2Cl[O3PCH2N(CH2CH2)2O][O3PCH2NH(CH2CH2)2O] 1 has been synthesized by hydrothermal reaction at 180 °C and structurally characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The interconnection of Zn(1)O4, Zn(2)O2NCl and CPO3 tetrahedra via corner-sharing forms a double layer structure with a channel system along b-axis direction. The result of connections in this manner is the formation of 8- and 16-atom windows that are parallel to one another and run in the a-axis direction. The morpholinyl groups of the ligands are orientated toward the interlayer space.A novel layered zinc phosphonate, Zn2Cl[O3PCH2N(CH2CH2)2O][O3PCH2NH(CH2CH2)2O] 1 has been synthesized by hydrothermal reaction at 180 °C and structurally characterized by single crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The interconnection of Zn(1)O4, Zn(2)O2NCl and CPO3 tetrahedra via corner-sharing forms a double layer structure with a channel system along b-axis direction. The result of connections in this manner is the formation of 8- and 16-atom windows that are parallel to one another and run in the a-axis direction. The morpholinyl groups of the ligands are orientated toward the interlayer space.
Keywords: Metal phosphonates; Crystal structure; Hydrothermal synthesis; Zinc;

Synthesis and electronic properties of double pincer-type cyclometalated iridium complexes by Daehyuk Choi; Taehyung Kim; Samala Malla Reddy; Jahyo Kang (41-44).
Double pincer-type cyclometalated iridium(III) complexes 24, 25, 26 and 27, (N^C^N^)2Ir and (C^N^N^)2Ir, were prepared based upon a few assumptions and their photophysical properties were examined.Double pincer-type cyclometalated iridium complexes were prepared based upon a few assumptions and their photophysical properties were examined.
Keywords: Double pincer; Spiro Ir complex; Iridium complex; Ancillary electron-carrier; Bis(imidazole)ligand;

A novel 3D coordination polymer [Cd154-Mtta)123-Mtta)63-SO4)43-OH)4]: Synthesis, structure and solid properties by You-Bang Ding; Ying Cheng; Zhi-Ling Zhang; Jing Zhang; Ye-Gao Yin; Wen-Hua Gao (45-47).
A solvothermal reaction of CdSO4 and NaN3 in H2O and CH3CN afforded a 3D coordination polymer with in situ formed 5-methyltetrazoles (Mtta) as multifunctional ligands, containing the chiral tricadmium clusters supported by Mtta’s, SO 4 2 - , and OH, as building blocks, and showing strong blue ambient fluorescence.A 3D coordination polymer, {[Cd154-Mtta)123-Mtta)63-SO4)43-OH)4] · 6H2O} n (1) (Mtta = 5-methyl-tetrazolate), which shows the rare multifunction of in situ formed Mtta and bright photo-induced blue emission, was isolated from a hydrothermal reaction of CdSO4  · 8/3H2O, NaN3 in acetonitrile and water.
Keywords: Cadmium (II); Tetrazole; Coordination polymer; In situ synthesis; Fluorescence;

A novel organo-functionalized mesoporous MCM-41 type of hybrid materials MCM–Si–DPBB and its ternary europium complex covalently bonded to the silica-based network MCM–Si–DPBB–Eu were synthesized and characterized. The hybrid material MCM–Si–DPBB–Eu has strong luminescence, and displays the emission of the Eu3+ 5D0-7F J (J  = 0, 1, 2, 3 and 4) transition lines due to the efficient energy transfer from the ligands to Eu3+.A novel organo-functionalized mesoporous MCM-41 type of hybrid materials MCM–Si–DPBB was synthesized by co-condensation of bidentate Si(OR)3 substituted N,N-2-diphenyloxyphosphine-4-bromomethyl-benzenamine (Si–DPBB) and tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as template. Its ternary europium complex covalently bonded to the silica-based network MCM–Si–DPBB–Eu was also prepared by introduction the Eu(DBM)3(H2O)2 into the hybrid materials. The hybrid material MCM–Si–DPBB–Eu has strong luminescence, and when excited by the ligands absorption wavelength (386 nm), it displays the emission of the Eu3+ 5D0-7F J (J  = 0, 1, 2, 3 and 4) transition lines due to the efficient energy transfer from the ligands to Eu3+.
Keywords: MCM-41; Luminescence hybrid materials; Covalently bonded; Europium complex;

Structure and photophysical properties of new trinuclear lanthanide complexes (Ln = Eu and Tb) with 1,10-phenanthroline by Ka-Leung Wong; Yi-Min Zhu; Yang-Yi Yang; Ga-Lai Law; Hai-Hua Fan; Peter A. Tanner; Wing-Tak Wong (52-54).
Examples of trinuclear lanthanide (Ln) complexes using bridging sulfato and hydroxo ligands for Ln = Eu and Tb are reported. Structural data demonstrate that in [Ln3(phen)3(OH)(SO4)4(DMF)3] · DMF · H2O, three nine-coordinate Ln3+ ions are caged in a monomeric structure with Ln⋯Ln distances slightly greater than 4 Å.Examples of trinuclear lanthanide (Ln) complexes using bridging sulfato and hydroxo ligands for Ln = Eu and Tb are reported. Structural data demonstrate that three nine-coordinate Ln3+ ions are caged in a monomeric structure in [Ln3(phen)3(OH)(SO4)4(DMF)3] · DMF · H2O, with Ln⋯Ln distances slightly greater than 4 Å. The luminescence and excitation spectra have been recorded and interpreted.
Keywords: Europium; Lanthanide complexes; Luminescence; Terbium; Trinuclear;

Silver(I) cis-diphenylphosphinoethylene complexes: Spectroscopic and structural characterization by Claudio Pettinari; Alessandro Marinelli; Adriano Pizzabiocca; Effendy; Brian W. Skelton; Allan H. White (55-57).
Adducts of the diphosphine cis-Ph2P(CH=CH)PPh2 (L) with AgX (X = NO3, BF4, ClO4 or CF3SO3) have been synthesized and characterized. AgNO3:L (2:1)2 is tetranuclear, derivative of the chair form, the bidentate ligands bridging central and peripheral silver centers.Adducts of the diphosphine cis-Ph2P(CH=CH)PPh2 (L) with AgX (X = NO3, BF4, ClO4 or CF3SO3) have been synthesized and characterized both in solution (1H, 31P NMR) and in the solid state (IR, single crystal X-ray structure analysis). The topologies of the structures in the solid state were found to depend on the nature of the counter-ion X. The adduct AgNO3:L (2:1)2 is tetranuclear, derivative of the chair form, the bidentate ligands bridging peripheral silver centers, the nitrates being coordinated through two oxygen atoms, the first O,O′-bridging the second bridging bidentate.
Keywords: Ag(I) complexes; Diphosphine ligands; X-ray; Spectroscopy;

Two novel complexes, [ZnL] n (1) and [Ag(HL)] n (2) (H2L = 4-[(1H-imidazol-4-yl)methylamino]benzoic acid) were synthesized under hydrothermal conditions. Complex 1 displays a rare three-dimensional (3,6)-connected rtl framework, while 2 has a one-dimensional chair-like structure including significant argentophilic Ag–Ag interactions.Complete and partial deprotonation of new ligand 4-[(1H-imidazol-4-yl)methylamino]benzoic acid (H2L) under hydrothermal conditions lead to the formation of two novel coordination polymers [ZnL] n (1) and [Ag(HL)] n (2). Complex 1 displays a rare three-dimensional (3,6)-connected rtl framework with (4 · 62)2(42  · 610  · 83) topology, while 2 has a one-dimensional chair-like structure including significant argentophilic Ag–Ag interactions. Both 1 and 2 show remarkable thermal stability and complex 1 was found to show strong blue luminescence with emission maxima at 381 nm upon excitation at 347 nm in the solid state at room temperature.
Keywords: Zinc(II) complex; Silver(I) complex; Hydrothermal reaction; Metal-organic framework; Photoluminescence property;

A new adjacent-bridged tetraaza macrotricycle (L2) has been prepared from the reaction of L1 with Br(CH2)3Br. In the presence of Cu(OAc)2  · H2O, L2 readily undergoes hydrolytic C–N bond cleavage under mild conditions to afford the macrobicyclic complex [CuL3]2+.A topologically constrained tetraaza macrotricycle, 2,2,4,10,10,12-hexamethyl-1,5,9,13-tetraazatricyclo[11.3.2.25.9]eicosane (L2), has been prepared by the reaction of 5,7,7,12,14,14-hexaazamethyl-1,4,8,11-tetraazacyclotetradecane (L1) with 1,3-dibromopropane. Interestingly, L2 reacts with Cu(OAc)2  · H2O to produce [CuL3]2+ (L3  = 2,2,4,10,10,12-hexamethyl-1,5,9,13-tetraazabicyclo[11.3.2]octadecane) as the only product under mild conditions, showing that the C–N bonds at one of the two N–CH2CH2–N linkages of the macrotricycle are readily broken in the presence of the metal salt. The complex [CuL3]2+ exhibits stronger ligand field strength than other related copper(II) complexes with a 5-6-6-6 chelate ring sequence and is unusually inert against decomposition in acid solutions.
Keywords: Adjacent-bridged macrocycle; Topologically constrained macrocycle; C–N cleavage; Copper(II) complex;