Inorganic Chemistry Communications (v.5, #1)

Gallium(III) and indium(III) complexes of cross-bridged tetraamine ligands by Weijun Niu; Edward H. Wong; Gary R. Weisman; Roger D. Sommer; Arnold L. Rheingold (1-4).
Gallium(III) and indium(III) complexes of cross-bridged cyclam and cyclen tetraaza macrocyclic ligands have been prepared and structurally characterized. In the crystalline state, both the GaCl3 (cross-bridged cyclam) and InBr3 (cross-bridged cyclen) complexes feature hexacoordinate cations in cis-folded tetradentate ligand clefts with ancillary cis-dihalides. These represent the first well-characterized gallium and indium halide complexes of tetraazamacrocycles.
Keywords: Gallium; Indium; Cyclam; Cyclen; Cross-bridged ligands;

Two novel heteroditopic ligands in which the bidentate 2,2-bipyridine (bpy) ligand is covalently linked to one or two 2,2:6,2″-terpyridine (terpy) terdentate ligands have been prepared and characterized. The synthesis and the physico-chemical features of their corresponding complexes in which the bpy site is complexed by a ruthenium moiety are also reported.
Keywords: 2,2-bipyridine; 2,2 : 6,2″-terpyridine ligand; Ruthenium complexes; Supramolecular structure;

The title complex was obtained by reacting [(η6-C6H6)(η6-C6Me6)2Ru32-H)33-O)]+ with RuCl3·nH2O in aqueous solution; it crystallises as the tetrafluoroborate salt. The cationic cluster is formed of two tetrahedral Ru4 substructures which are held together by two chloro bridges.
Keywords: Cluster; Octanuclear; Terahedral; Ruthenium; Arene ligand; Oxo cap;

Reaction of the symmetrical proligand H3L with bis(acetylacetonato)zinc(II) has given the homodinuclear complex [Zn2L(acac)]·CH3CN in which one of the pendant phenolato groups functions as a bridge for the dinuclear zinc centre. The complex crystallises in the triclinic space group P-1, with unit cell parameters a=10.0250(11) Å, b=10.6132(13) Å, c=19.139(2) Å, α=80.418(2)°, β=75.792(2)°, γ=84.532(2)°.
Keywords: Crystal structure; Phenolato-bridge; Zinc(II) complex;

Treatment of the ruthenium complex cation [(η 6-C6H3Me3-1,3,5)(RuCl(dfppe)]+ {dfppe=(C6F5)2PCH2CH2P(C6F5)2} with proton sponge yields [{η 6,η 1,η 1-C6H3Me-5-[CH2-2-C6F4P(C6F5)CH2]2-1,3}RuCl]+ by stepwise intramolecular dehydrofluorinative carbon–carbon coupling.
Keywords: Ruthenium; η 6-Arene; Phosphine; Dehydrofluorinative carbon–carbon coupling; Hybrid ligands;

The new heterotrinuclear complex [Cu2Zn(NH3)I3(Me2Ea)3] was prepared for the first time from copper and zinc powders, ammonium iodide and 2-dimethylaminoethanol (HMe2Ea) in methanol in air. X-ray crystallographic analysis reveals the asymmetric Cu2ZnO3I core with the structure that can be described as a distorted cube missing one corner. The μ-alkoxo- and μ-iodo-bridging between metal centres results in copper–copper and two copper–zinc separations being 3.353(2), 3.197(2) and 3.225(2) Å, respectively.
Keywords: Mixed-metal complexes; Heterotrinuclear complex; Zero-valent copper; Zero-valent zinc; Ammonium iodide; 2-Dimethylaminoethanol; Crystal structure;

Isopolyoxorhenates observed by positive ion electrospray mass spectrometry by Frans Sahureka; Robert C Burns; Ellak I von Nagy-Felsobuki (23-27).
Unknown positive ion isopolyoxorhenates have been observed using electrospray ionization mass spectrometry (ESI+). The ESI+ studies of ammonium and alkali metal (Na+ and K+) perrhenate salts in aqueous solution at pH 4.5 show the existence of the series [A x+1ReVII x O4x ]+ (where x=1–5 and A=NH4 +, Na+ and K+). In the potassium perrhenate system, the series [K x+2ReVReVII x O4x+3]+ (x=0–4) has also been characterised. All of these four series have {AReO4} as the aggregation unit. In the ammonium perrhenate system, the monomeric Re(VII)-containing species, [(NH4)2(H2ReO5)]+, [(NH4)3(HReO5)]+ and [(NH4)4(ReO5)]+ were also detected.
Keywords: Electrospray mass spectrometry; Isopolyoxorhenates; Polyoxometalates; Rhenium(VII);

Two-dimensional rare earth coordination polymers involving different coordination modes of thiodiglycolic acid by Yuan-Zhu Zhang; Jun-Ran Li; Song Gao; Hui-Zhong Kou; Hao-Ling Sun; Zhe-Ming Wang (28-31).
Two coordination polymers [La2(tdga)3(H2O)2] n (1) and {[Pr2(tdga)3(H2O)2]·H2O} n (2) were obtained by the reaction between Ln(OH)3 (Ln=La, Pr) and thiodiglycolic acid (H2tdga=H2S(CH2CO2)2), which have a novel double-layered and a single-layered structure, respectively. In the complexes, new coordination modes of the ligand were observed.
Keywords: Coordination polymer; Coordination modes; Double-layered structure; Lanthanide;

Optically active triosmium cluster with bridging terpenic thioureato-like ligand – synthesis, structure, and absolute configuration by Vladimir P. Kirin; Vladimir A. Maksakov; Alexander V. Virovets; Sergey A. Popov; Alexey V. Tkachev (32-34).
The reactions of (3bS,4aR)-3,4,4-trimethyl-3b,4,4a,5-tetrahydro-cyclopropa[3,4]cyclopenta[1,2-c]pyrazole-1-carbothioic acid (2-methoxy-phenyl)-amide (amide 1) containing a thiourea-like fragment >N–C(S)NHR with triosmium clusters Os3(CO)12−n (NCMe) n (n=1,2) and (μ-H)Os3(CO)10(μ-OH) result in the formation of diastereomers with the μ2 chelate-bridging by S and pyrazole N atom ligands. X-ray analysis of one of the diastereomers was performed and its absolute configuration was determined.
Keywords: Optically active triosmium clusters; Terpenes; X-ray structure; Absolute configuration;

The hydro(solvo)thermal reaction of 4-quinolinecarbaldehyde with Cd(ClO4)2·6H2O yields a one-dimensional linear chain metal–organic coordination polymer with carboxylate-bridged and μ2-OH2: [Cd(μ2-H2O) (4-quinolinecarboxylato-O, O)2] 1 which is characterized by single crystal X-ray determination and IR. Crystallographic data for 1, C20H14CdN2O5, monoclinic, space group C2/c, a=15.368(2), b=14.399(2), c=7.7969(11)  A ̊ , β=92.507(3)°, Z=4, V=1723.7(4)  A ̊ 3 .
Keywords: Crystal structure; One-dimensional chain; Cd(II)complex; 4-quinolinecarboxylate; Hydro(solvo)thermal synthesis;

Synthesis, characterization and crystal structure of a zinc bis-dithiocarboxylate derivative by Donald J. Darensbourg; M. Jason Adams; Jason C. Yarbrough (38-41).
The zinc(II) complex, Zn(3,5-di-t-butyl-4-hydroxybenzene-dithiocarboxylate)2(pyridine) (3) was obtained by the reaction of Zn(CH3CN)4(BF4)2 with the sodium salt of 3,5-di-t-butyl-4-hydroxybenzene-dithiocarboxylate (1) with subsequent recrystallization from pyridine. The latter salt (1) was prepared by the deprotonation of 2,6-di-t-butylphenol with NaH in THF, followed by reaction with carbon disulfide at ambient temperature. The structure of complex 3 was established by X-ray crystallography and shown to be of a distorted trigonal bipyramidal geometry with one sulfur atom from each of the dithiocarboxylate ligands occupying the axial sites. By way of contrast, Na(2,4-di-t-butylphenolate) was found to react with CS2 to afford the xanthate derivative, Na(O-2,4-di-t-butylphenyldithiocarbonate) (4).

Design of molecular rectangles by using compartmental and exo-bidentate ligands by Diana Visinescu; Marius Andruh; Achim Müller; Marc Schmidtmann; Yves Journaux (42-45).
Molecular rectangles with different sizes can be obtained by reacting a binuclear copper(II) complex, [L(μ-OH)Cu2](ClO4)2 (L=the compartmental end-off ligand, 2,6-bis[N-(2-pyridylethyl)formimidoyl]-phenolato), with bis-(4-pyridyl) derivatives (4,4-bipyridine, 1,2-bis(4-pyridyl)ethylene). Two tetranuclear complexes have been obtained and characterized by single-crystal X-ray diffraction: [{L(μ-OH)Cu2}-(μ-4,4-bipy)2-{Cu2(μ-OH)L}](ClO4)4·3H2O (1), and [{L(μ-OH)Cu2}-(μ-bpe)2-{Cu2(μ-OH)L}](ClO4)4·4H2O (2). Compounds 1 and 2 have been obtained also through a multicomponent self-assembly process, namely by mixing together the stoichiometric amounts of compartmental Schiff base, exo-bidentate ligand and lithium hydroxide, followed by the addition of copper(II) perchlorate.
Keywords: Schiff bases; Copper complexes; Tetranuclear complexes; Molecular rectangles;

Acid-catalyzed self-alkylation of FcCH2NHPh. Solid-state structures of FcCH2NHPh and (FcCH2)NPh by Tomáš Baše; Ivana Cı́sařová; Petr Štěpnička (46-50).
N-(ferrocenylmethyl)aniline (2) readily undergoes an acid-catalyzed self-alkylation to give a mixture of N,N-bis(ferrocenylmethyl)aniline (3) and aniline. In the alkylation reaction, amine 2 acts as the alkylated nucleophile as well as a source of the alkylating species, the ferrocenylmethylium cation, after protonation. Solid-state structures of amines 2 and 3 were determined by X-ray diffraction.
Keywords: Ferrocene; Schiff base; Amines; Alkylation; Crystal structure;

Synthesis, structure and magnetic property of a new oxo-centered mixed-valent trinuclear manganese complex by Jun Li; Fengxing Zhang; Qizhen Shi; Jing Wang; Yu Wang; Zhongyuan Zhou (51-55).
A mixed-valent trinuclear μ3-oxo bridged manganese complex [Mn3O(O2CCH2Cl)6(Py)2(H2O)]·0.5C5H5N was synthesized. Its crystal structure was determined, together with the results of variable temperature magnetic susceptibility, cyclic voltammogram and IR spectrum.
Keywords: Mixed-valent; Trinuclear manganese complex; Crystal structure; Preparation;

Synthesis of copper(II)–lanthanum(III) complex of a dinucleating macrocycle and its hydrolytic property for 4-nitrophenylphosphate by Kazuhiro Manseki; Osamu Nakamura; Kohei Horikawa; Masatomi Sakamoto; Hiroshi Sakiyama; Yuzo Nishida; Yoshihiko Sadaoka; Hisashi Okawa (56-58).
Cu(II)La(III) complex of a dinucleating macrocycle derived from the (2:2) condensation of 2,6-diformyl-4-methylphenol and 1,3-propanediamine was synthesized and its hydrolytic activity toward 4-nitrophenylphosphate (NPP) was examined in aqueous DMF (DMF:water=9:1) as the first study using d–f heterodinuclear complex. From the comparison of results of the Cu(II)La(III) complex with those of mononuclear La(III), dinuclear Cu(II)Cu(II) and mononuclear Cu(II) complexes, it was suggested that the CuLa heterometal center cooperatively functions in the NPP hydrolysis.
Keywords: Cu(II)La(III) complex; Heteronuclear complex; Hydrolysis; 4-Nitrophenylphosphate;

The first supramolecular assemblies comprised of dimetal units and chiral dicarboxylates by F.Albert Cotton; James P. Donahue; Carlos A. Murillo (59-63).
The first molecules containing metal–metal bonded Mo2 4+ units linked by chiral dicarboxylates have been prepared and characterized by X-ray crystallography and 1H NMR spectroscopy; the compounds [Mo2(DAniF)3]2(dicarboxylate), 1 for l-tartrate and 2 for d-aspartate (DAniF=N,N -di-p-anisylformamidinate) represent a first step toward the synthesis of more complex polygonal structures assembled from M2 units and chiral linkers.
Keywords: Chiral; Supramolecular assemblies; Molybdenum–molybdenum quadruple bonds;

Reaction of the ligand α,α-bis(N-1,4,7-triazacyclononane)-m-xylene (XYL-tacn) with copper(II) chloride and sodium hexafluorophosphate in acetonitrile/methanol leads to the assembly of a remarkable tetranuclear copper(II) complex. The crystal structure and magnetic properties of the novel tetranuclear Cu(II) complex are reported. The complex exhibits an unusual [(CuCl)4(μ-Cl)2] binding mode with a Cu··· Cu distance of 6.856(3) Å.
Keywords: Crystal structures; Copper(II) complexes; Tetranuclear complexes; Chloro complexes;

The synthesis of new cyclopalladated compounds by reaction between palladium acetate and the potentially tridentate imines 4-ClC6H4CHN(CH2) n NMe2 (n=2,3) in acetic acid is described. The experimental data suggest a dinuclear structure for the complexes, with a bridging CNN ligand. 1 H NMR spectra of these complexes in CD3COOD solution, indicate the existence of three different species in equilibrium.
Keywords: Palladacycles; Tridentate imines; Mass spectrometry; Solution behaviour;

Synthesis and DNA binding behavior of a dipyridocatecholate bridged dicopper(II) complex by Jian-Zhong Wu; Hong Li; Jian-Guo Zhang; Jin-Hong Xu (71-75).
1,10-Phenanthroline-5,6-diol (dpcatH2) was prepared conveniently from 1,10-phenanthroline-5,6-dione using hydrazine sulfate as reductant, and a new bimetallic Cu(II) complex, [(phen)Cu(dpcat)Cu(phen)](ClO4)2, where phen denotes 1,10-phenanthroline was synthesized by a “one-pot” method. Presence of calf thymus DNA would result in an evident change in the electronic absorption, quenching effect on the fluorescence, protection from fluorescence quencher ferrocyanide and disappearance of redox process of the complex, and the viscosity of DNA would be enhanced by addition of the complex. All these facts suggest that the dicopper(II) complex binds to double helix DNA by classical intercalation.
Keywords: Dinuclear copper(II) complex; 5,6-dihydroxy-1,10-phenanthroline; DNA; Spectroscopy;

A new supramolecular octanuclear copper(II) complex, {[Cu(sae)]42CH3OH·H2O}2, has been synthesized and structurally characterized. The structure of the complex consists of two tetracopper(II) cubane units related by hydrogen bonds.
Keywords: Schiff base; Copper; Crystal structure; Supramolecule;

Expanded hexadentate ligands of Jäger type: synthesis and X-ray analysis by Jörg Wagner; Helmar Görls; Heike Keutel (78-81).
The free ligand 2 of Jäger type was synthesized via demetallation of the copper complex 1. 2 was expanded by condensation with dicarbonyl compounds to yield further hexadentate ligands with [N4O2]-donorset suitable for transition metal complexation. The structures of 2 and 3 were described by NMR and X-ray analysis.
Keywords: Hexadentate ligand; Expanded ligand; Schiff base; Demetallation; X-ray analysis;

Mononuclear, binuclear, and trinuclear transition-metal allenyl and/or propargyl complexes are reviewed with respect to methods of synthesis, structure, and reaction chemistry. Structural relationships among the various types of complexes are presented and, to the extent possible, used to rationalize some patterns of reactivity. Recent developments in the field are accorded special emphasis.
Keywords: Allenyl complexes; Propargyl complexes; Binuclear complexes; Trinuclear complexes; Mixed-metal complexes; Synthesis;