Inorganic Chemistry Communications (v.9, #2)

Contents List (iii-xi).

Insertion of terminal aliphatic alkynes into the Pt–H bond of the heterobimetallic hydride complex [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(H)(PPh3)] (1) affords as minor isomer the μ-vinylidene compounds [(OC)3Fe(μ-C=C(H)R)(μ-dppm)Pt(PPh3)] (2) and as major isomer the dimetallacyclopentenone complexes [(OC)2Fe(μ-C(=O)CR=CH)(μ-dppm)Pt(PPh3)] (3).Insertion of aliphatic 1-alkynes such as tert-butylacetylene, 1-hexyne or 1,6-heptadiyne into the Pt–H bond of the heterobimetallic hydride complex [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(H)(PPh3)] (1) (dppm = Ph2PCH2PPh2) leads to the formation of an isomeric mixture of μ-vinylidene complexes [(OC)3Fe{μ-C=C(H)R}(μ-dppm)Pt(PPh3)] (2a: R =  tert-Bu, 2b: R =  n-Bu, 2c: R = (CH2)3–CCH) and dimetallacyclopentenones [(OC)2Fe{μ-C(=O)CR=CH}(μ-dppm)Pt(PPh3)] (3a: R =  tert-Bu, 3b: R =  n-Bu, 3c: R = (CH2)3–CCH). The molecular structures of 2a and 3c have been determined by single-crystal X-ray diffraction.
Keywords: Heterobimetallics; Hydride; Alkyne; Insertion; μ-Vinylidene; Iron; Platinum;

Radical-dependent magnetic interactions in two 1-D copper(II) complexes with nitronyl nitroxide and imino nitroxide radicals bridged by iminodiacetate anion by Dong-Zhao Gao; Jing Chen; Shu-Ping Wang; You Song; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan (132-135).
Two novel 1-D chain copper(II) complexes were synthesized and characterized structurally and magnetically. The two complexes crystallize in neutral 1-D chains, where Cu(II)–nitroxide cationic units are linked by iminodiacetate anion ligands. The radical-dependent magnetic properties are discussed.Two novel one-dimensional (1-D) chain complexes [Cu(NIT3Py)(ida)] n (1) and [Cu(IM4Py)(ida)] n (2) (NIT3Py = 2-(3′-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, IM4Py = 2-(4′-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and ida = iminodiacetate anion), were synthesized and characterized structurally and magnetically. The two complexes crystallize in neutral 1-D chains, where Cu(II)–nitroxide cationic units are linked by iminodiacetate anion ligands. The magnetic measurements show that complex 1 exhibits ferromagnetic coupling, while complex 2 exhibits antiferromagnetic interactions between the Cu(II) ion and the nitroxide radical.
Keywords: Crystal structure; Copper complex; Nitronyl nitroxide; Imino nitroxide; Magnetic properties;

A new synthetic route to pentacarbonylalkene complexes of tungsten(0), employing, as a source of pentacarbonyltungsten moiety, the binuclear complex of tungsten(I) [(μ-GeCl2){W(CO)5}2], was used in the synthesis of a thermally labile ethene complex [W(CO)52-C2H4)] (1). The molecular structure of compound 1 was determined by single-crystal X-ray diffraction studies.The new method of synthesis, employing the binuclear complex of tungsten(I) [(μ-GeCl2){W(CO)5}2] as a source of pentacarbonyltungsten moiety, was used in synthesis of a thermally labile ethene complex of tungsten(0). The crystal structure of [W(CO)52-C2H4)] (1) has been established by X-ray diffraction studies.
Keywords: Tungsten; Ethene complex; Crystal structure;

Reactivity of bis(ferrocenyl)ethynylthioether towards triruthenium dodecacarbonyl by Esther Delgado; Elisa Hernández; Miriam Menacho; Regina Muñoz (139-142).
New ruthenium carbonyl compounds containing organosulfur ligands, have been obtained by cleavage and formation of S–C and C–C bonds in the thioether FcCCSCCFc towards Ru3(CO)12.New ruthenium compounds have been prepared by rupture and formation of S–C bonds as well as coupling between alkyne groups with or without insertion of CO, in the reaction of FcCCSCCFc with Ru3(CO)12. All complexes have been characterized by analytical and spectroscopic data and the crystal structure of [Ru3(CO)93243-{FcCC(C2Fc)SC(Fc)CSCCFc}) has been solved by X-ray diffraction.
Keywords: Ruthenium carbonyls; Thioether; Alkynethiolate;

TlI three-dimensional coordination polymer involving tetranuclear cubic cage nodes, [Tl48-SB)2] n (1) [H2SB = 4-[(4-hydroxyphenyl)sulfonyl]-1-benzenol]The single crystal X-ray analysis of a novel TlI coordination polymer of 4-[(4-hydroxyphenyl)sulfonyl]-1-benzenol (H2SB) ligand shows that the complex is a three-dimensional polymer as a result of bridging “SB2−” ligands with basic repeating [Tl48-SB)2] units. There are four thallium atoms with different coordination spheres in the cubic cage. These thallium atoms contain irregular coordination sphere with stereo-chemically active lone pair and thallium–thallium interactions, Tl(1)O4, Tl(2)O4Tl2, Tl(3)O4Tl and Tl(4)O3Tl.
Keywords: Thallium; 4-[(4-hydroxyphenyl)sulfonyl]-1-benzenol; Lone pair; 3D Coordination polymer;

The crystal structure of [Cu2(phen)(μ-H2PO4-O,O′)2(H2PO4)2][Cu2(phen)2(μ-H2PO4-O,O′)(μ-H2PO4-O)(μ-HPO4-O)]2(H2O)9 containing the phen ligand with mono- and di-dentate H 2 PO 4 - and monodentate HPO 4 2 - oxoanions is reported. Two crystallographically independent dinuclear units with different bridging properties of (di)hydrogenphosphato anions are found in this compound. The two Cu(II) ions in the first unit, [Cu2(phen)(μ-H2PO4-O,O′)2(H2PO4)2], are bridged by two didentate bridging dihydrogenphosphato monoanions with two non-bridging monovalent dihydrogenphosphato anions. The Cu–Cu distance is 5.043(3) Å. The magnetic susceptibility measurement (5–300 K) revealed a weak antiferromagnetic interaction between the Cu ions in one dinuclear unit with J 1  = −8.2 cm−1 and a very weak ferromagnetic interaction in the other dinuclear unit with J 2  = 0.96 cm−1.The crystal structure of a copper(II) complex containing the ligand 1,10-phenanthroline (phen) with mono- and di-dentate H 2 PO 4 - and monodentate HPO 4 2 - oxoanions, [Cu2(phen)(μ-H2PO4-O,O′)2(H2PO4)2][Cu2(phen)2(μ-H2PO4-O,O′)(μ-H2PO4-O)(μ-HPO4-O)]2(H2O)9, is reported and determined by X-ray crystallography. Two crystallographically independent dinuclear units with different bridging properties of (di)hydrogenphosphato anions are found in this compound.The two Cu(II) ions in the first unit, [Cu2(phen)(μ-H2PO4-O,O′)2(H2PO4)2], are bridged by two didentate bridging dihydrogenphosphato monoanions and also contains two non-bridging monovalent dihydrogenphosphato anions. The geometry of the Cu(II) ions is square pyramidal with a Cu–Cu distance of 5.043(3) Å.The two Cu(II) ions in the second unit, [Cu2(phen)2(μ-H2PO4-O,O′)(μ-H2PO4-O)(μ-HPO4-O)], are bridged by three different hydrogenphosphate anions; a didentate bridging dihydrogenphosphate monoanion, a monodentate dihydrogenphosphate bridging monoanion and a monodentate hydrogenphosphate dianion. This bridging mode is unique and has not been reported so far for dinuclear Cu(II) compounds. The geometry of the Cu(II) ions in this second unit is distorted square pyramidal and the Cu–Cu distance is 3.074(3) Å.The magnetic susceptibility measurement (5–300 K) have been fitted with two different J values. A weak antiferromagnetic interaction between the Cu ions in one dinuclear unit with J 1  = −8.2 cm−1 and a very weak ferromagnetic interaction between the Cu ions in the other dinuclear unit with J 2  = 0.96 cm−1, allow an acceptable fit.
Keywords: Crystal structure; Copper(II); Dihydrogenphosphate complex; Magnetic properties;

The synthesis and structural characterization of novel N-meta-ferrocenyl benzoyl dipeptide esters by David Savage; Steven R. Alley; John F. Gallagher; Alok Goel; Paula N. Kelly; Peter T.M. Kenny (152-155).
N-meta-ferrocenyl benzoyl dipeptide ethyl esters (25) have been prepared by coupling meta-ferrocenyl benzoic acid (1) to the dipeptide ethyl esters using the conventional 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxybenzotriazole (HOBt) protocol. The dipeptides employed were GlyGly(OEt) (2), GlyAla(OEt) (3), GlyLeu(OEt) (4) and GlyPhe(OEt) (5). The compounds were structurally characterized by a combination of NMR spectroscopic techniques and mass spectrometry (MALDI-MS, ESI-MS).A series of novel N-meta-ferrocenyl benzoyl dipeptide esters (25) have been prepared by coupling meta-ferrocenyl benzoic acid (1) to the dipeptide ethyl esters using the conventional 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxybenzotriazole (HOBt) protocol. The dipeptides employed were GlyGly(OEt) (2), GlyAla(OEt) (3), GlyLeu(OEt) (4) and GlyPhe(OEt) (5). The compounds were fully characterized by a range of NMR spectroscopic techniques and by mass spectrometry (MALDI-MS, ESI-MS).
Keywords: Ferrocene; Bioorganometallic chemistry; Dipeptides; MALDI;

Unusual addition of but-2-yne to a permethyltitanocene species by Karel Mach; Róbert Gyepes; Jiří Kubišta; Michal Horáček (156-159).
Two molecules of but-2-yne add to a permethyltitanocene species generated in the [TiCl25-C5Me5)2]/Mgexcess/thf system to give compound 1.The [TiCl25-C5Me5)2]/Mgexcess/tetrahydrofuran system reacts with but-2-yne in excess to give paramagnetic (η51-1,2,3,4-tetramethyl-5-(2,3,4,5-tetramethylpenta-2,4-dien-1,5-diyl-κC5)cyclopentadienyl)(η5-pentamethylcyclopentadienyl)titanium(III) (1) as the main product. The crystal structure of 1 shows a minimum steric hindrance between the methylated cyclopentadienyl ligands and non-coplanar conjugated double bonds in the C5 tether.
Keywords: Titanium; Permethyltitanocene; But-2-yne; Insertion; Titanium(III) complex; ESR spectra; X-ray crystallography;

Novel results on thiodiacetate zinc(II) complexes: Synthesis and structure of [Zn(tda)(phen)]2  · 5H2O by Abdessamad Grirrane; Antonio Pastor; Eleuterio Álvarez; Carlo Mealli; Andrea Ienco; Agustı́n Galindo (160-163).
The zinc thiodiacetate complex [Zn(tda)(H2O)] n (1) ( tda = S ( CH 2 COO ) 2 2 - ) is obtained from the reaction of zinc dichloride with a 1:1 mixture of Na2CO3 and thiodiacetic acid in aqueous solutions. This hydrate tda complex is novel and it differs significantly from another known hydrate derivative, namely [Zn(tda)(H2O)3] · H2O. The reaction of 1 with o-phenanthroline (phen) gave the dinuclear compound [Zn(tda)(phen)]2  · 5H2O (2), which was identified by X-ray analysis.Novel zinc thiodiacetate complex [Zn(tda)(H2O)] n (1) ( tda = S ( CH 2 COO ) 2 2 - ) was obtained from the reaction of aqueous solutions of zinc dichloride with a 1:1 mixture of Na2CO3 and thiodiacetic acid. Complex 1 is a different hydrate compound with respect to the known species [Zn(tda)(H2O)3] · H2O. The selective formation of 1 or [Zn(tda)(H2O)3] · H2O can be achieved by controlling the crystallization conditions and it is even possible to interconvert the two hydrate compounds by fast or slow crystallization processes. The reaction of 1 with o-phenanthroline (phen) gave the dinuclear compound [Zn(tda)(phen)]2  · 5H2O (2), which was identified by X-ray analysis. The water crystallization molecules are interconnected by hydrogen bonds and they are aligned inside channels, which are parallel to the c-axis.
Keywords: Zinc(II); Thiodiacetate; Thiodiglycolate; Crystal structure;

Interaction of lysozyme during calcium carbonate precipitation at supramolecular level by Lin Yang; Lan She; Jian-Guo Zhou; Ying Cao; Xiao-Ming Ma (164-166).
Lysozyme was used as a matrix to control the crystallization of CaCO3 and the effect of CaCO3 on the secondary structure of lysozyme was studied by FT-IR spectra. The experimental results indicate that there is supramolecular interaction between lysozyme and CaCO3.Interaction of lysozyme during calcium carbonate precipitation at supramolecular level was studied. The results showed that the aragonite phase of calcium carbonate was formed under the direction of lysozyme and the aragonite had also an important effect on the secondary structure of lysozyme. These results may be explained by supramolecular interaction between lysozyme and CaCO3.
Keywords: Supramolecular interaction; Biomineralization; Calcium carbonate; Lysozyme;

Single crystal X-ray study on a novel terephthalato-(μ2-tp)-bridged binuclear Cu(II) tetraaza macrocyclic complex, [Cu2(dinemac)2(tp)(ClO4)2], reveals that the synanti disposition of two NO2 groups in the individual dinemac ligand and consequent intermolecular H-bonding between the two successive binuclear entities on both sides results a supramolecular R 2 2 (34) synthon in (0 1 1) plane which on further propagation in the same sequence renders two single strand helices connected via tp moiety results in a 3-D supramolecular helical ladder-like assembly.Single crystal X-ray study on a novel terephthalato-(μ2-tp)-bridged binuclear Cu(II) tetraaza macrocyclic complex, [Cu2(dinemac)2(tp)(ClO4)2], reveals that the synanti disposition of two NO2 groups in the individual dinemac ligand and consequent intermolecular H-bonding between the two successive binuclear entities on both sides results a supramolecular R 2 2 (34) synthon in (0 1 1) plane which on further propagation in the same sequence renders two single strand helices connected via tp moiety results a 3-D supramolecular helical ladder-like assembly.
Keywords: Terephthalate-(μ2-tp)-bridging; Binuclear Cu(II) complex; Tetraaza macrocycle; R 2 2 (34) synthon; Helical ladder-like assembly;

[Ni2([22]-HMTADO)(CN)2] · 0.5H2O is prepared by reacting [Ni2([22]-HMTADO)(OH2)2]Cl2  · H2O with an aqueous solution of NaCN. The green polymeric single crystal of {[Ni6([22]-HMTADO)3(CN)4][Ni(CN)4] · 5H2O · 8CH3OH} n suitable for X-ray diffraction study is grown from methanolic solution of [Ni2([22]-HMTADO)(CN)2] · 0.5H2O over 2 mon at room temperature.The nickel(II) polymeric complex {[Ni6([22]-HMTADO)3(CN)4][Ni(CN)4] · 5H2O · 8CH3OH} n (III), where H2[22]-HMTADO = 5,5,11,17,17,23-hexamethyl-3,7,15,19- tetraazatricyclo[19,3,1,19,13] hexacosa-1(25),2,7,9,11,13(26),14,19,21,23-decane-25,26-diol, is obtained from methanolic solution of [Ni2([22]-HMTADO)(CN)2] · 0.5H2O (II) by slow evaporation method and characterized by X-ray crystal structure determination. The nickel(II) centers in the oxa-azamacrocyclic complex are bridged by the two phenolate oxygens as well as by CN and coordinated to carbon and nitrogen atoms derived from the bridging cyano ligand, forming square pyramidal and octahedral geometries, respectively. The mean nonbonded Ni⋯Ni intermetallic separation in the polymeric complex is 3.159 Å.
Keywords: Oxa-azamacrocyclic complex; Dinuclear nickel(II) complex; Bridging cyano ligand;

A new copper(II) complexes of 14-membered hexaaza macrocyclic ligands; 3,10-dialkyl-dibenzo-1,3,5,8,10,12-hexaazacyclotetradecane, [Cu(R2Bzo2[14]aneN6)]2+ (R = H, Me, Et, Bu, Benzyl); have been prepared by the in situ one-pot template synthesis (IOPTS) of formaldehyde and 1,2-phenylenediamine with alkyl or benzyl amine in the presence of copper(II) ion. The complexes of a hexaaza macrocycle have been characterized by elemental analyses, IR, FAB, UV–Vis, and H NMR spectroscopy, conductometric and magnetic measurements.A new copper(II) complexes of 14-membered hexaaza macrocyclic ligands; 3,10-dialkyl-dibenzo-1,3,5,8,10,12-hexaazacyclotetradecane, [Cu(R2Bzo2[14]aneN6)]2+ (R = H, Me, Et, Bu, Benzyl); have been prepared by the in situ one-pot template synthesis (IOPTS) of formaldehyde and 1,2-phenylenediamine with alkyl or benzyl amine in the presence of copper(II) ion. The complexes of a hexaaza macrocycle have been characterized by elemental analyses, IR, FAB, UV–Vis, and H NMR spectroscopy, conductometric and magnetic measurements.
Keywords: Template synthesis; Hexaaza; Copper(II); Macrocycle; 14-Membered;

Synthesis and characterization of a highly topologically constrained tetraazamacrocyclic ligand by Rhett T. Watson; Chuanjiang Hu; Donald G. VanDerveer; Derek T. Musashe; Paul S. Wagenknecht (180-182).
A macrocyclic ligand with two 1,5-diazacyclooctane (daco) rings joined by two ethylene bridges has been prepared and structurally characterized. The free ligand is flexible and takes on a “pinwheel” conformation.A macrocyclic ligand with two 1,5-diazacyclooctane (daco) subunits joined by two ethylene bridges (1,4,8,11-tetraazatricyclo[9.3.3.34,8]eicosane) has been prepared and characterized. Each of the daco subunits takes on the chair/boat conformation in the free ligand.
Keywords: Constrained macrocycle; Tetraazamacrocycle; Topological constraint; 1,5-Diazacyclooctane; Daco;

A novel mixed valence tetranuclear nitrosyl complex bridged by tetraoxomolybdate by Toshiaki Yonemura; Tomoko Hashimoto; Mayumi Hasegawa; Tamami Ikenoue; Tomoharu Ama; Hiroshi Kawaguchi (183-186).
The reaction of the molybdenum–dinitrosyl complexes with PPh3, using 2-pyrimidinethiolate (pymt) or 2-pyridinethiolate (pyt) as a thiolate ligand, was found to produce a dinuclear complex [{(ON)MoL2}2(μ-OH)2] (1) (L = pymt or pyt) and Ph3PO. In addition, the first reported example of a mixed valence molybdenum–nitrosyl tetranuclear complex, [Ph3POH]2[{(ON)Mo(pymt)2}2(μ-MoO4)2] (2), was produced by the reaction of 1(pymt) with Ph3PO. This is the first published nitrosyl complex containing both tetraoxomolybdate and thiolato ligands. The molybdenum and bridging oxygen atoms formed a novel eight-membered ring with a central porous structure.The reaction of the molybdenum–dinitrosyl complexes with PPh3, using 2-pyrimidinethiolate (pymt) or 2-pyridinethiolate (pyt) as a thiolate ligand, was found to produce a dinuclear complex [{(ON)MoL2}2(μ-OH)2] (1) (L = pymt or pyt) and Ph3PO. In addition, the first reported example of a mixed valence molybdenum–nitrosyl tetranuclear complex, [Ph3POH]2[{(ON)Mo(pymt)2}2(μ-MoO4)2] (2), was produced by the reaction of 1(pymt) with Ph3PO. This is the first published nitrosyl complex containing both tetraoxomolybdate and thiolato ligands. The molybdenum and bridging oxygen atoms formed a novel eight-membered ring with a central porous structure.
Keywords: Molybdenum–nitrosyl complex; Mixed valence tetranuclear complex; Thiolato complex; Denitrosyl reaction;

A new subphthalocyanine complex, bromo[tri-α-(2,4-dimethyl-3-pentyloxy)subphthalocyanine]boron, has been synthesized and its third-order nonlinear optical (NLO) properties in ethanol solution have been studied by Z-scan technique using 8 ns laser pulses at 532 nm. The results reveal that the new complex exhibits strong NLO absorption effect and self-focusing refractive performance.A new subphthalocyanine complex, bromo[tri-α-(2,4-dimethyl-3-pentyloxy)subphthalocyanine]boron, has been synthesized and characterized by elemental analysis, MALDI-TOF-MS, FT-IR and UV–vis spectroscopy. Its third-order nonlinear optical (NLO) properties in ethanol solution have been studied by Z-scan technique using 8 ns laser pulses at 532 nm. The results reveal that the new complex exhibits strong NLO absorption effect (α 2  = 3.7 × 10−10  m W−1) and self-focusing refractive performance (n 2  = 2.1 × 10−17  m2  W−1). The effective third-order NLO susceptibility (χ (3)) and the molecular second-order hyperpolarizability (γ) value were calculated to be 1.12 × 10−11 and ∼6.8 × 10−28  esu, respectively. All of the values are comparable to those of the reported good NLO materials. In addition, the effects of cone-shaped molecular structure and axially heavy-atom (Br) substitution on third-order NLO properties are discussed.
Keywords: Synthesis; Subphthalocyanine; Z-scan; Third-order optical nonlinearity; NLO;

Two novel complexes [Ni2(H2O)2(H2TTHA)] · 6H2O (1), and {[Cu3(H2O)4(TTHA)] · 8H2O} n (2) were synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, IR and UV–vis spectra. 1 is a binuclear complex while 2 exhibits one-dimensional (1D) coordination polymer.Two novel complexes [Ni2(H2O)2(H2TTHA)] · 6H2O (1), and {[Cu3(H2O)4(TTHA)] · 8H2O} n (2) were synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, IR and UV–vis spectra. 1 is a binuclear complex while 2 exhibits one-dimensional (1D) coordination polymer.
Keywords: Triethylenetetraaminehexaacetic acid; Nickel(II) complex; Copper(II) complex; Crystal structure;

Ferromagnetic coupling in two chain-like nickel(II) tricyanomethanide complexes with polyamines as co-ligands by Jun Luo; Ze-Huai Shao; En-Qing Gao; Chuan-Feng Wang; Rui-Fang Cai; Xi-Geng Zhou (196-200).
Two novel ferromagnetic nickel(II) tricyanomethanide complexes {[Ni(tmeda)(tcm)(H2O)](tcm)} n (1) and [Ni(dien)(tcm)2] n (2) (tmeda = tetramethylethylenediamine, dien = diethylenetriamine and tcm = tricyanomethanide) have been synthesized and structurally characterized.Two new chain-like nickel(II) tricyanomethanide complexes {[Ni(tmeda)(tcm)(H2O)](tcm)} n (1) and [Ni(dien)(tcm)2] n (2) (tmeda = tetramethylethylenediamine, dien = diethylenetriamine, tcm = tricyanomethanide) have been synthesized and characterized by single crystal X-ray diffraction. Magnetic studies indicate that there are ferromagnetic couplings between adjacent NiII ions in 1 (θ  = 7.3 K, C = 0.96 cm3  mol−1  K) and 2 (θ  = 1.9 K, C = 1.07 cm3  mol−1  K), respectively.
Keywords: Tricyanomethanide; Polyamines; Nickel(II) complex; Crystal structures; Ferromagnetic coupling; Coordination polymer;

A 3D porous coordination polymer, Zn5(OH)4(BDC)3  · 2DMF (1), has been synthesized, and characterized by single crystal X-ray diffraction analysis and thermal analyses, which indicate the solvent molecules are removable and the evacuated framework exhibits reversible sorption–desorption behaviors.A 3D porous coordination polymer, Zn5(OH)4(BDC)3  · 2DMF (1), has been synthesized, and characterized by single crystal X-ray diffraction analysis and thermal analyses, which indicate the solvent molecules are removable and the evacuated framework exhibits reversible sorption–desorption behaviors.
Keywords: Coordination polymer; Porous; X-ray diffraction; Sorption;

Treatment of the methanolic solution of H3L (H3L = 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxy-phenyl) -3-azabut-3-enyl]-1,3-imidazoline) and ZnSO4  · 7H2O affords the multiplex [Zn2(SO4)(L)]2[Zn(H2O)6] · 3H2O · 0.75CH3OH (1), which gives the first example of anionic complex of L3− and shows photoluminescence at room temperature.Treatment of the methanolic solution of 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxy-phenyl)-3-azabut-3-enyl]-1,3- imidazoline (H3L) and ZnSO4  · 7H2O affords the solvated multiplex [Zn2(SO4)(L)]2[Zn(H2O)6] · 3H2O · 0.75CH3OH (1) which uniquely contains anionic dizinc complexes of L3− as components and shows photoluminescence at room temperature.
Keywords: Zinc complex; Schiff base; Crystal structure; Photoluminescence;

A new facile high yield preparative route for mixed-trinuclear acetate clusters by Heron Vrubel; Tai Hasegawa; Elisabeth de Oliveira; Fábio S. Nunes (208-211).
Homometallic clusters can be isolated from a clean reaction between the metal hydroxide and acetic acid. The heterobimetallic compounds were obtained by the reaction of the iron(III) or vanadium(III)-homometallic cluster, in water, with an excess of iron(II), cobalt(II) and nickel(II) acetates. The new route gives pure products with much higher yields when compared with the classical methods. The compounds were characterized by atomic absorption and elemental analysis, electrochemistry and IR spectroscopy.The cluster compounds [FeIII 3O(CH3CO2)6(H2O)3]CH3COO, [FeIII 2FeIIO(CH3COO)6(H2O)3], [FeIII 2CoIIO(CH3COO)6(H2O)3], [FeIII 2NiIIO(CH3COO)6(H2O)3], [VIII 2FeIIO(CH3COO)6(H2O)3] and [VIII 2CoIIO(CH3COO)6(H2O)3 were prepared by new synthetic routes. Homometallic clusters can be isolated from a clean reaction between the metal hydroxide and acetic acid. The heterobimetallic compounds were obtained by the reaction of the iron(III) or vanadium(III)-homometallic cluster, in water, with an excess of iron(II), cobalt(II) and nickel(II) acetates. The new route give pure products with much higher yields when compared with the classical methods. The compounds were characterized by atomic absorption and elemental analysis, electrochemistry and IR spectroscopy.
Keywords: Mixed-trinuclear acetate clusters; New synthetic routes; Infrared; Electrochemistry;

Copper(II) and cobalt(II) coordination polymers with azido ions and 1,3-bis(4′-pyridyl)propane by En-Qing Gao; Yan-Xia Xu; Ai-Ling Cheng; Ming-Yuan He; Chun-Hua Yan (212-215).
Inorganic copper(II)-azido chains, in which the single end-to-end azido bridges propagate weak ferromagnetic coupling, are built into a two-dimensional coordination network with flexible organic linkers. Conformational supramolecular isomerism was observed in cobalt(II) systems.A copper(II) complex [Cu(μ-1,3-N3)(N3)(bpp)] n (1) (bpp = 1,3-bis(4′-pyridyl)propane) has been shown to exhibit a two-dimensional network formed by the bpp ligands interlinking copper(II)-azido chains, in which the single azido bridge assumes an asymmetric μ-1,3 mode and mediates weak ferromagnetic coupling. On the other hand, the reaction of cobalt(II), azido and bpp yielded two supramolecular isomers of [Co(N3)2(bpp)2] n (2 and 3) in which the azido ions serve as terminal ligands and the metal ions are linked by the bpp ligands in different conformations.
Keywords: Coordination polymers; Azide; Magnetic properties; Crystal structures; Supramolecular isomerism;

Two silvers(I) supramolecular isomers {[Ag(bbta)(NO3)] · H2O} n (1), and [Ag(bbta)(NO3)]2 (2) have been synthesized. 1 forms novel one-dimensional concavo-convex chain. However, 2 contains the neutral dimer Ag2(bbta)2 18-membered metallacycle. The luminescent spectra of 1 and 2 in the solid state and in DMF solution at room temperature were determined.Two silvers(I) supramolecular isomers {[Ag(bbta)(NO3)] · H2O} n (1), and [Ag(bbta)(NO3)]2 (2) have been synthesized in the different solvent systems by using the flexible ligand 1,2-bis(benzotriazol-1-yl)ethane (bbta). 1 forms novel one-dimensional concavo-convex chain. However, 2 contains the neutral dimer Ag2(bbta)2 18-membered metallacycle. The bbta ligands exhibit the anti and gauche conformations in 1 and 2, respectively. 1 and 2 are both the topological isomers and conformation isomers. The luminescent spectra of 1 and 2 in the solid state and in DMF solution at room temperature were determined.
Keywords: Flexible bis(benzotriazole) ligands; Supramolecular isomers; Silver complex; Luminscence; Concavo-convex chain; Dimer metallacycle;

2-D zinc coordination polymer with ellipse-like channels and blue fluorescence by Ling Xu; Bing Liu; Guocong Guo; Jin-shun Huang (220-222).
A 2-D novel framework {[Na2Zn53-OH)2(BTB)4(H2O)4][Zn(H2O)6]} n  · 6nH2O obtained from the diffusion method with blue fluorescence, is constructed from the interconnection of subunits of [Zn2(BTB)2] with the linker of [Zn(μ3-O)2] subunits.A 2-D novel coordination polymer {[Na2Zn53-OH)2(BTB)4(H2O)4][Zn(H2O)6]} n  · 6nH2O, (H3BTB = 1,2,3-benzenetricarboxylic acid) is obtained from the diffusion method. BTB3− adopts two kinds of μ5 coordination modes to bridge the zinc(II) centers to form a 2-D network with approximate ellipse-like channels. The framework is constructed from the interconnection of [Zn2(BTB)2] subunits with the linker of [Zn(μ3-O)2] subunits. The compound produces blue fluorescence with emission at 420 nm possibly assigned to LMCT.
Keywords: Zinc; 1,2,3-Benzenetricarboxylic acid; Diffusion; Structure; Fluorescence;

Two novel asymmetric dicyanophenoxy-derivatised iron (III) and Co(II) porphyrin complexes have easily been electropolymerised onto glassy carbon electrodes. The thin solid films exhibited excellent stability and electrocatalysis towards the direct detection of important analytes such as nitrite, nitric oxide, and hydrogen peroxide in aqueous solutions.Solution and solid phase electrochemical features of 5-[4-(3,4-dicyanophenoxy)phenyl],10,15,20-triphenylporphyrin complexes of iron(III) (FeCNOTPP(Cl)) and cobalt(II) (CoCNOTPP) have been described. These novel asymmetric dicyanophenoxy-derivatised cobalt and iron porphyrin complexes were electropolymerised onto glassy carbon electrodes, which in aqueous solutions, gave surface concentrations (ca. 10−10  mol cm−2) typical of monolayer coverages. The films also exhibited excellent stability and electrocatalysis towards the direct detection of important analytes as nitrite, nitric oxide, and hydrogen peroxide in aqueous solutions.
Keywords: Iron and cobalt dicyanophenoxy-derivatised porphyrins; Electropolymerisation; Hydrogen peroxide; Nitrite; Nitric oxide; Chronoamperometry;

Styrene polymerization with organoeuropium compounds containing pyrazinamide by Renata Diana Miotti; Alessandra de Souza Maia; Janaína Gonçalves Rodrigues; Wanda de Oliveira (228-230).
Organoeuropium compounds EuCl2Cp(PzA)2 and EuCp(MS)2(PzA)2 (MS = methanesulfonate, CH 3 SO 3 - ), PzA = pyrazinamide, were active in styrene polymerization, when methylaluminoxane (MAO) was used as co-catalyst. The catalytic systems produced atactic polystyrene with activities up to 5.65 kg(PS) mol(Eu)−1  h−1 (EuCl2Cp(PzA)2, Al/Eu = 700, T  = 60 °C, t  = 4 h) in the absence of toluene.Organoeuropium compounds EuCl2Cp(PzA)2 and EuCp(MS)2(PzA)2 (MS = methanesulfonate =  CH 3 SO 3 - ), PzA = pyrazinamide were active in styrene polymerization, when methylaluminoxane (MAO) was used as co-catalyst. The catalytic systems produced polystyrene with activities up to 5.65 kg(PS) mol(Eu)−1  h−1 (EuCl2Cp(PzA)2, Al/Eu = 700, T  = 60 °C, t  = 4 h) in the absence of toluene. The presence of solvent decreased catalytic activity. The compound containing MS anion presented lower catalytic activities. Polystyrene obtained is atactic and presents average molar mass of 3.0 kg/mol.
Keywords: Organolanthanides; Pyrazinamide; Styrene polymerization; Methanesulfonate; Chloride;

Copper(II) complex of a tridentate N-donor ligand with unexpected Cu–H interaction by Bernadette S. Creaven; Mary F. Mahon; John McGinley; Ann-Marie Moore (231-234).
A new pyridine–amine ligand has been prepared and its reaction with copper perchlorate characterised. An interesting phenyl-H–Cu interaction was observed.The new pyridine–amine ligand, meophdpa (bis(dipyridylmethyl)-4-methoxyaniline) was synthesised and reacted with copper(II) perchlorate. The X-ray crystal structure of the resulting complex revealed a monomeric copper(II) site, with the copper bound to the three ligand nitrogens in a relatively unusual meridional fashion, as well as a chloride and a water molecule. The sixth coordination site was, unexpectedly, occupied by a phenyl ring hydrogen atom.
Keywords: Tridentate pyridine–amine ligand; Synthesis; Copper(II) complex; X-ray crystal structure;

Pyrazolyl coordination polymers of cadmium(II) by P.B. da Silva; R.C.G. Frem; A.V.G. Netto; A.E. Mauro; J.G. Ferreira; R.H.A. Santos (235-238).
The polymers [Cd(μ-Cl)2(pyrazole)2] n (1) and [Cd(μ-1,3-SCN)2(pyrazole)2] n (2) have been prepared and characterized. Both complexes exhibited chain structures made by linear arrays of Cd(II) bridged by chloro (1) or inversely related 1,3-SCN groups (2). Intermolecular hydrogen bonds and another non-covalent interactions are responsible for the self-assembly of linear chains into 2D networks.The coordination polymers [Cd(μ-Cl)2(HPz)2] n (1) and [Cd(μ-1,3-SCN)2(HPz)2] n (2) (HPz = pyrazole) have been prepared and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction. Both complexes exhibited chain structures made by linear arrays of Cd(II) bridged by chloro (1) or inversely related 1,3-SCN groups (2) and the pyrazole ligands at the apical sites. Intermolecular hydrogen bonds and another non-covalent interactions are responsible for the self-assembly of linear chains into 2D networks.
Keywords: Coordination polymers; Pyrazole; Cadmium(II); Thiocyanate; Non-covalent interactions; Self-assembly;

A simple determination of alkylsilane monolayer population density by John C. Linehan; Cory M. Stiff; Glen E. Fryxell (239-241).
Silane population density of a variety of organosilane-based monolayers on silica nanoparticles were determined using solid-state 29Si NMR.Silane population density of a variety of organosilane-based monolayers on silica nanoparticles were determined using solid-state 29Si NMR.
Keywords: Silane; Monolayer; Population; NMR;

A new unique tetranuclear Cu(II) compound with double bridging thiocyanate anions: Synthesis, X-ray structure and magnetism of [Cu41,3-NCS)6(dpyam)4(O2CH)2(H2O)2] (dpyam = di-2-pyridylamine) by Sujittra Youngme; Jaturong Phatchimkun; Unchulee Suksangpanya; Chaveng Pakawatchai; Gerard A. van Albada; Manuel Quesada; Jan Reedijk (242-247).
A new unique tetranuclear copper(II) complex doubly-bridged by thiocyanate anions, [Cu41,3-NCS)6(dpyam)4(O2CH)2(H2O)2 (dpyam = di-2-pyridylamine) has been synthesized and characterized by X-ray diffraction methods and magnetic measurements. The “outer” Cu ions, with a CuN3O(S, O) chromophore, have an axially elongated octahedral geometry. The axial positions are occupied by an oxygen atom of a water molecule (Cu–O distance 2.518(1) Å) and by a sulfur atom of a bridging thiocyanate anion at a semi-coordination distance of 3.048(1) Å. The “inner” Cu atoms, with a CuN4(S2) chromophore do also have an axially elongated octahedral geometry. The axial positions are occupied by two sulfur atoms of two bridging thiocynate anions (Cu–S semi-coordinating distances are 2.875(1) and 3.126(1) Å). Each Cu ion is bridged by two μ1,3-NCS anions (in an equatorial-axial bridging mode) forming in this way a zigzag tetranuclear unit. The magnetic susceptibility data of the compound have been investigated between 5 and 200 K. The compound shows a very weak antiferromagnetic interaction between the Cu ions, in agreement with the non-overlapping magnetic orbitals of each Cu ion.A new unique tetranuclear copper(II) complex doubly-bridged by thiocyanate anions [Cu41,3-NCS)6(dpyam)4(O2CH)2(H2O)2 (dpyam  = di-2-pyridylamine) has been synthesized and characterized by X-ray diffraction methods and magnetic measurements.The “outer” Cu ions, with a CuN3O(S, O) chromophore, have an axially elongated octahedral geometry. The basal plane of these outer Cu(II) ions consist of 2 nitrogen atoms of the dpyam ligand with Cu–N distances of 1.980(2) and 2.008(2) Å, one nitrogen atom of a bridging thiocyanate anion (Cu–N distance 1.961(3) Å) and an oxygen atom of a formate molecule (Cu–O distance 1.977(1) Å). The axial positions are occupied by an oxygen atom of a water molecule (Cu–O distance 2.518(1) Å and by a sulfur atom of a bridging thiocyanate anion at a semi-coordination distance of 3.048(1) Å.The “inner” Cu atoms, with a CuN4(S2) chromophore do also have an axially elongated octahedral geometry. The basal plane is formed by 2 nitrogen atoms of the dpyam ligand with Cu–N distances of 1.995(2) and 2.018(3) Å and two nitrogen atoms of two bridging thiocyanate anions (Cu–N distances 1.946(3), 1.976(3) Å). The axial positions are occupied by two sulfur atoms of two bridging thiocynate anions (Cu–S semi-coordinating distances are 2.875(1) and3.126(1) Å). Each Cu ion is bridged by two μ1,3-NCS anions (in an equatorial-axial bridging mode) forming in this way a zigzag tetranuclear unit.The magnetic susceptibility data of the compound have been investigated between 5 and 200 K. The compound shows a very weak antiferromagnetic interaction between the Cu ions, in agreement with the non-overlapping magnetic orbitals of each Cu ion.
Keywords: Copper(II); Crystal structure; EPR; Magnetism; Di-2-pyridylamine; Thiocyanate-bridging ligands;

The complex tetraphenylcyclobutadiene palladium(IV) chloride shows a longest-wavelength absorption at λ max  = 530 nm which is assigned to a LMCT transition from the C4Ph4 dianion to Pd(IV). LMCT excitation leads to the release of Pd(CH3CN)2Cl2 and neutral C4Ph4 which dimerizes to octaphenylcyclooctatetraene.The complex tetraphenylcyclobutadiene palladium(IV) chloride shows a longest-wavelength absorption at λ max  = 530 nm which is assigned to a LMCT transition from the C4Ph4 dianion to Pd(IV). LMCT excitation leads to the release of Pd(CH3CN)2Cl2 and neutral C4Ph4 which dimerizes to octaphenylcyclooctatetraene.
Keywords: Electronic spectra; LMCT; Palladium; Cyclobutadiene complexes; Photochemistry;