Inorganic Chemistry Communications (v.3, #6)

The assembly of TlTp4Bo and M(Tp4Bo)2 (M e.g. Co, Ni) in the crystal is dictated by aromatic ππ and C–H⋯π interactions. This leads to the formation of chiral C 2-symmetrical pairs (for Tl) or solvent-filled, about 30%-porous, non-covalent framework structures (for Co and Ni). The potassium salt KTp4Bo features a κN,η-C–C,η2-C–N cation-π coordination mode — curious for a Tp-type ligand.
Keywords: Crystal structures; π–π interactions; Framework structures; Indazolylborate ligand; Transition metal complexes; Supramolecular assembly;

Synthesis and X-ray characterization of the new pentanickel cluster cation [Ni55-S)(μ3-S)22-S)(μ-CH3COO)(PPh3)5]+ by Franco Cecconi; Carlo A. Ghilardi; Stefano Midollini; Annabella Orlandini; Alberto Vacca (276-280).
By reacting Ni(CH3COO)2·6H2O with H2S in the presence of PPh3, the new Ni/S cluster of formula [Ni55-S)(μ3-S)22-S)(μ-CH3COO)(PPh3)5]PF6·C7H8·0.5CH2Cl2 has been isolated and characterized by X-ray diffraction analysis. Crystal data: space group P21/c, a=15.774(4), b=21.235(7), c=29.288(7) Å, β=95.66(4)°. The inner core consists of a square pyramid of five nickel atoms, linked together by a bridging acetate and four variously bridging sulfur ligands. The 31P{1H} NMR spectra in dichloromethane solution are consistent with the above geometry.
Keywords: Crystal structures; Nickel complexes; Chalcogen complexes; Cluster complexes;

As part of our study on oxomolybdenum(V) complexes we present here the synthesis and crystal structure of a novel dimeric oxomolybdate(V) [Mo2O4(acac)2thala]·3C2H5OH (acac=acetylacetonato, thala=3-(2-thienyl)-dl-alanine) in which two molybdenum atoms are being bridged not only by two oxo-oxygens but additionally by the amino acid carboxylate group. Two octahedrally coordinated molybdenum atoms are singly bonded to each other at a distance of 2.5631(5) Å.
Keywords: Crystal structures; Molybdenum complexes; Oxo complexes; Amino acid complexes;

Reactivity of [WCl(SnCl3)(CO)3(NCMe)2] towards t BuCCH. by Izabela Czeluśniak; Tadeusz Głowiak; Teresa Szymańska-Buzar (285-288).
In the reaction of [WCl(SnCl3)(CO)3(NCMe)2] with tert-butylacetylene the very labile bis(alkyne) complex [WCl(SnCl3)(CO)( t BuCCH)2(NCMe)] has been observed as the major product by means of IR and NMR spectroscopy. The latter compound in reaction with two equivalents of PPh3 in CH2Cl2 solution gives very poorly soluble purple crystals of the tungsten(II) cationic complex. The crystal structure of this compound consists of the discrete [SnCl6]2− anion, two independent [WCl(CO)( t BuCCH)(NCMe)(PPh3)2]+ cations and four MeCN (solvent) molecules. This is the first crystallographically characterized cationic chlorocarbonyl complex of tungsten(II) containing a terminal alkyne as ligand.
Keywords: Crystal structures; Tungsten(II) complexes; Tin(IV) complexes; Alkyne complexes;

New half-sandwich nickel(II) complex with mono-hydrotris(3,5-dimethylpyrazolyl)borate ligand and nitrite by Ying-Ji Sun; Peng Cheng; Shi-Ping Yan; Zong-Hui Jiang; Dai-Zheng Liao; Pan-Wen Shen (289-291).
This paper presents the syntheses, crystal structure and properties of a new half-sandwich mononuclear nickel(II) complex containing a single hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) ligand and nitrito and methanol co-ligands, [Tp*NiII(η 2-O2N)(CH3OH)]. The complex crystallizes in the triclinic system, space group P 1 ̄ (No. 2), a=10.0669(11), b=10.1132(11), c=11.8420(12) Å, α=76.895(2), β=73.234(2), γ=62.470(2)°, Z=2, R 1=0.0458, wR 2=0.1187. The Ni(II) ion in the complex is coordinated to three pyrazolyl nitrogen atoms, two oxygen atoms of NO2 and one oxygen atom of CH3OH to form a distorted octahedron. The NO2 was coordinated in an asymmetric nitrito-O,O′-bidentate coordination mode with an O(1)–Ni–O(2) angle of 57.71(11)° and Ni–O bond lengths of 2.1882 and 2.1222 Å.
Keywords: Crystal structures; Nickel(II) complexes; Hydrotris(pyrazolyl)borate ligands; Nitrite complexes;

Silsesquioxane chemistry, 6  1 Part 5 is Ref. . 1 by Volker Lorenz; Axel Fischer; Frank T. Edelmann (292-295).
The compound [Cy7Si7O12BeLi]2·2THF (3) was prepared in high yield by reacting in situ prepared Cy7Si7O9(OLi)3 (2) with anhydrous BeCl2 in THF at 20°C. The molecular structure of 3 has been determined by X-ray diffraction and is the first structurally characterized silsesquioxane derivative of beryllium. In the solid state, self-assembly leads to the formation of a dimeric molecule.
Keywords: Crystal structures; Beryllium complexes; Lithium complexes; Silsesquioxane complexes;

Synthesis and structural characterisation of new binuclear Pd(II) complexes with both bridging and terminal pyrazolate ligands by Josefina Pons; Arafa Chadghan; Jaume Casabo; Angel Alvarez-Larena; Joan Francesc Piniella; Josep Ros (296-299).
Dinuclear pyrazolato-bridged Pd(II) complexes Pd2L4 0 and Pd2L4 1 have been prepared by reacting Pd(Ac)2 and one equivalent of HL0 (3-phenyl-5-(2-pyridyl)pyrazole) or HL1 (3-phenyl-5-(6-methyl-(2-pyridyl))pyrazole. The new complexes have been characterised by elemental analyses, IR, 1H NMR and in the case of PdL1 4 by single crystal X-ray diffraction methods. This structure shows two palladium atoms bridged by two L1 ligands. The square-planar geometry of each Pd atom is completed by a bidentate chelating L1 ligand. The six-membered dipalladacycle formed by the two Pd atoms and the two bridging pyrazolato ligands adopts a distorted boat-like conformation.
Keywords: Palladium complexes; Dinuclear complexes; Pyrazole complexes; Crystal structures;

A cyanohydridoborato–vanadium(II) complex, trans-[V(NCBH3)2(thf)4] by Ronald Hedelt; Carola Schulzke; Dieter Rehder (300-302).
[V(NCBH3)2(thf)4], the first cyanohydroborato complex of an early transition metal, has been generated in the system [V(CO)6]/I2/tolane/Na[NCBH3] in THF. The crystal structure reveals an ideal trans configuration (point group D 2h ) with about linear CNBH3 units, and without intermolecular (hydrogen bonding) interactions.
Keywords: Cyanohydroborato complexes; Tetrahydrofurane complexes; Vanadium complexes; Crystal structures;

Preparation, solution behaviour and X-ray crystal structure of [PtOTf(triphos)]OTf by G Annibale; P Bergamini; V Bertolasi; M Cattabriga; V Ferretti (303-306).
The lability of the coordinated triflate in the new complex [PtOTf(triphos)]OTf both in the solid state and in solution is pointed out by the X-ray crystal structure, by NMR observations and by some examples of nucleophilic substitution at platinum.
Keywords: Crystal structures; Platinum complexes; Triphosphine complexes; Triflate complexes;

The cleavage of plasmid DNA by a dinuclear copper(II) complex of 1,2,4,5-tetrakis(1′-amino-3′-thiabutyl)benzene is promoted significantly (rate constant of 3.3×10−5 s−1 at pH 7.8 and 37°C) compared with the essentially inactive mononuclear copper(II) complex of the analogue 1,2-bis(1′-amino-3′-thiabutyl)benzene (rate constant <10−10 s−1). This implies that the two copper ions in close proximity and acting synergetically are important in accelerating cleavage, and separate roles for the two coppers in the dimer are proposed.
Keywords: DNA hydrolysis; Catalysed cleavage; Dicopper(II) complexes; Aminothioether ligand;

DFT (density functional theory) calculations have revealed that the position of the proton of the hydroperoxide adduct of an Fe(III)–porphyrin compound influences greatly the electron density of the oxygen atoms of the peroxide ion, suggesting that the position of the proton in the hydroperoxo–iron(III) compound plays an important role in controlling the electronic interaction between the hydroperoxide adduct and the porphyrin system (OOH–π interaction).
Keywords: Role of proton; Activation of oxygen in oxygenase; Heme-containing oxygenase; OOH–π interaction;

AgCN·2AgNO3 (1) contains a linear [AgCN] chain that essentially retains the characteristics of neat silver cyanide, with two Ag–ONO2 fragments weakly bound to each head-turned-tail disordered cyanide group (Ag2–C1=2.598(4) Å). In AgCN·2AgClO4·2H2O (2), the [AgCN] chain takes a zigzag configuration with Ag(H2O) fragments attached to both sides, resulting in a μ41κC:η1κN coordination mode for each ordered cyanide ion. The zigzag chains are cross-linked by O–H⋯O hydrogen bonds to form a close-packing of elongated hexagonal channels, with ordered perchlorate anions accommodated in double columns inside each channel.
Keywords: Silver; Cyanide; Double salt; Perchlorate;

Zr33-O){[CH2C(CH3)2O]2}4 {[HO(CH3)2CCH2C(CH3)2O]}2 was prepared by a transesterification reaction between Zr(O-n-Pr)4 and 2,4-dimethylpentane-2,4-diol, DMPDH2. The product was obtained as a white crystalline solid containing discrete molecules of a μ3-O bridged trizirconium cluster with one chelating DMPD, two chelating DMPDH groups and three exobidentate DMPD groups, with one end bonded to a single Zr atom and the other bridging adjacent Zr atoms. The two chelating DMPDH groups form strong hydrogen bonds to the oxygen atoms of the chelated DMPD group.
Keywords: Zirconium alkoxides; Transesterification reactions; MOCVD precursors;

The first ladder-like lanthanide double chain complex [Tm(NTA)(H2O)2]·2H2O (H3NTA=nitrilotriacetic acid) by Yu Chen; Bao-Qing Ma; Qin-De Liu; Jun-Ran Li; Song Gao (319-321).
The title complex has been synthesized in aqueous solution and its crystal structure was determined by X-ray diffraction. It consists of a one-dimensional ladder-like chain. One carboxyl group bridges the adjacent Tm ions giving rise to the edge of the ladder, a second one links the Tm ions from the neighboring edge in zigzag form to act as the rung of the ladder, and a third one monodentately coordinates with Tm to serve as the pendant of the ladder. Each Tm ion is eight coordinated by one nitrogen atom, five oxygen atoms from three NTA molecules and two oxygen atoms from H2O.
Keywords: Rare earth complexes; Nitrilotriacetate (NTA); Ladder-like chain; Crystal structures;

The copper(II) complex [Cu(salgly)(bpy)]·4H2O (1), where salgly is a tridentate glycinatosalicylaldimine Schiff base ligand, is prepared and structurally characterized. The complex is found to be catalytically active in the oxidation of ascorbic acid by dioxygen and the process is also effective in the presence of benzylamine giving benzaldehyde as a product, thus modeling the activity of the CuB site of dopamine β-hydroxylase.
Keywords: Copper(II) complexes; Schiff-base complexes; Dopamine β-hydroxylase model; Catalytic properties; Ascorbate oxidation;

Synthesis and structure of {η3-MeSi(CH2SPh)3}Cr(CO)3: how long can a Cr(0)–S(thioether) bond length be? by William C. Blackwell III; Dmitry Bunich; Thomas E. Concolino; Arnold L. Rheingold; Daniel Rabinovich (325-327).
The new tridentate thioether ligand MeSi(CH2SPh)3 has been prepared in good yield and its first transition metal derivative, the octahedral chromium tricarbonyl complex {η3-MeSi(CH2SPh)3}Cr(CO)3, has been synthesized and fully characterized. In agreement with the reduced basicity of arylthioethers and the expected lability of their metal complexes, the new complex exhibits the longest Cr(0)–S(thioether) bond distances observed to date.
Keywords: Chromium complexes; Thioether complexes; Crystal structures; Tris(thioether)silane;

In the presence of Bun 4NBr acting as a phase-transfer reagent, organophosphoryl derivatives of tungstophosphate of formula [α 2-R2P2W17O61]6− (R=C6H11P(O) (1); C6H5P(O) (2); C6H11P(S) (3); C6H5P(S) (4)) have been prepared and characterized by elemental analysis, IR, 31P and 183W NMR spectroscopy. The nine-line 183W spectrum indicates the hybrid anion possesses C s symmetry in CH3CN–CD3CN.
Keywords: Polyoxometalate; Organophosphorus; NMR (31P,183W); Synthesis;

Two complexes, W3Te7[(EtO)2PS2]3I (1) and W3Te7[(PriO)2PS2]3I (2), were prepared via solid state reaction of (RO)2PS2K with a product of high temperature reaction of elemental W, Te and I2. The structures of the two compounds have been determined by X-ray crystallography. Crystal data are 1: monoclinic, P21/c, Z=4, a=14.3862(3), b=16.2114(1), c=18.9766(2) Å, β=111.655(1)°, V=4113.37(10) Å3, Z=4, D c=3.435 Mg/m3; 2: monoclinic, P21/n, Z=4, a=14.6197(3), b=23.9630(1), c=15.1249(3) Å, β=113.688(1)°, V=4852.28(14) Å3, Z=4, D c=3.027 Mg/m3. The results of both the complexes present the first examples of a cluster containing a [W33-Te)(μ2-Te2)3]4+ core.
Keywords: Cluster compounds; Tungsten complexes; Tellurium-rich compounds; Crystal structures;