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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

November 2016 issue

Special issue on Scorpionates: a golden anniversary

Guest Editors: Glenn Yap (University of Delaware, USA) and Kiyoshi Fujisawa (Ibaraki University, Japan)

Highlighted illustration

Cover illustration: The year 2016 marks the 50th anniversary of the discovery of scorpionates by Jerry Trofimenko. The papers in this special issue clearly show that scorpionate chemistry remains relevant, exciting, and productive.

editorial


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The Guest Editors of the special issue entitled `Scorpionates: a golden anniversary', Glenn Yap and Kiyoshi Fujisawa, introduce the collection of invited papers celebrating the 50th anniversary of the discovery of scorpionate chemistry and highlight the current productive state of the subject.

scorpionates: a golden anniversary


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The structure of a new mononuclear bis­muth(III) complex with the soft scorpionate ­(3-tert-butyl-2-sulfanyl­idene-1H-imidazol-1-yl)hydro­borate ligand is compared with that of the binuclear derivative.

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Two new homodinuclear tris­(3-alkyl­pyrazol­yl)borate complexes of CoII and NiII with a tetra­acetyl­ethane dianion as the bridging ligand were synthesized and characterized by mass spectrometry and X-ray crystallography. A significant deviation from orthogonality between the acetyl­acetonate planes was observed in the two complexes.

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The structures of thallium(I) complexes with two different mesityl-substituted ligands, i.e. tris(3-mesityl-5-methylpyrazol-1-yl)hydroborate and bis(3-mesityl-5-methylpyrazol-1-yl)(5-mesityl-3-methylpyrazol-1-yl)hydroborate, are compared. The shape of the former thallium(I) complex can be considered as a vase and the latter as a baseball glove.

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Although [hydro­tris­(3-phenyl­pyrazol­yl)borato]nickel(II) (denoted TpPhNiII) complexes can have biological significance as metalloenzyme models, none have been reported. To provide insight into the coordination environment afforded by this ligand, three TpPhNiII complexes with aryl­oxides of varying steric and electronic effects are compared.

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In the novel iron(II) complex salt tetra­phenyl­phospho­nium tris­(thio­cyanato)[1,1,1-tris­(pyridin-2-yl)ethane]­ferrate(II), the Fe—N bond lengths indicate that the specimen consists of comparable molar fractions of the low- and high-spin species at 296 K. A magnetic study confirmed that spin-crossover takes place around 290 K.

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Two atypical tris­pyrazolylborate ligands were selected to make a heteroscorpionate complex in order to showcase the flexibility of steric and electronic effects easily afforded by this class of facial tridentate ligands.

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The structural characterization of the tris(1-tert-butyl-2-mercaptoimidazol­yl)hydro­borate, [Tm^{{\rm Bu}^{\rm t}}], complexes Cp[κ3S2,H-Tm^{{\rm Bu}^{\rm t}}]MCl2 (M = Zr and Ti) by X-ray diffraction demonstrates that the [Tm^{{\rm Bu}^{\rm t}}] ligand coordinates in a κ3S2,H mode, while the benzyl compounds [Tm^{{\rm Bu}^{\rm t}}]M(CH2Ph)3 (M = Zr and Hf) exhibit κ3S3 coordination.

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Thallium(I) and cobalt(II) halide complexes of the ferrocenyltris(3-R-pyrazol­yl)borate ligand (FcTpR, with R = iPr or tBu) have been synthesized and their structural characteristics determined to expand the range of redox-active third-generation scorpionates.

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The different motifs present in the Cambridge Structural Database concerning tetra­kis­pyrazolylborates have been analyzed and two new structures, a Tl+ and a K+ salt, resolved. Compared with the previously reported motifs, one of them is new.

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The heteroditopic Bipy–CH2–O–CH2–C(pz)3 ligand (Bipy-L; Bipy is 2,2′-bi­pyridine and pz is pyrazol­yl) reacts with AgI and ReI metallic centers to yield the {[Ag(μ-Bipy-L)]BF4·0.5Et2O}n coordination polymer and the [ReBr(Bipy-L)(CO)3] monometallic compound.

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The cadmium(II) complex of the tetra­topic ligand 1,2,4,5-C6H2[CH2OCH2C(pz)3]4 (pz is pyrazolyl) consists of a one-dimensional coordination polymer, {1,2,4,5-C6H2[(CH2OCH2C(pz)3]4Cd2(BF4)4}n, showing infinite chains of 32-atom metallomacrocycles.

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Bis[tetra­kis­(3-methyl-1H-pyrazol-1-yl)borato]samarium(II) was synthesized by the reaction of SmI2 with potassium tetra­kis­(3-methyl­pyrazol­yl)borate in tetrahydrofuran. The X-ray structure analysis revealed an unusual side-on coordination mode of a 3-methyl­pyrazolyl group through an N=N group in the B(3-Mepz)4 ligand. The distortion is defined by the B—N—N—Sm torsion angle [85.5 (4)°].

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Three N atoms from the facially capping tridentate chelating tris­(4,4-di­methyl­oxazolin-2-yl)phenyl­borate ligand and a chloride ligand coordinate an NiII ion in a highly distorted tetra­hedral geometry. The Ni—Cl bond length [2.1851 (5) Å] is comparable to those found in a previously reported tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borate derivative [2.1955 (18) and 2.150 (2) Å]. The mol­ecular structure deviates from C3v symmetry due to the structural flexibility of the tris­(4,4-di­methyl­oxazolin-2-yl)phenyl­borate ligand.

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A new procedure for the synthesis of the electron-poor ligand tris­(3,4,5-tri­bromo­pyrazol-1-yl)phosphine oxide is described. The structure displays a network of halogen bonds in the solid state.

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Tris(pyrazol­yl)borate complexes of rhodium are well known to activate C—H bonds. The reactive [Tp′Rh(PMe3)] fragment [Tp′ is tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borate] is found to react with valero­nitrile to give a κ1N-bound complex. In contrast to the widespread evidence for the reaction of this fragment with C—H bonds via oxidative addition, no evidence for such a complex is observed.

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The silver(I) adduct [HB{3-(CF3),5-(CH3)Pz}3]AgNCCH3 was obtained by treating [HB{3-(CF3),5-(CH3)Pz}3]Na with CF3SO3Ag in the presence of aceto­nitrile, and was isolated in 85% yield. Single-crystal X-ray diffraction analysis reveals that the AgI center has a pseudo-tetra­hedral all-nitro­gen coordination sphere and is supported by a tris­(pyrazol­yl)borate ligand that binds to the AgI center in a κ3-fashion.

research papers


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The chemically analogous chloride and bromide complexes NHC–Au–Cl and NHC–Au–Br (NHC is an N-heterocyclic carbene) have significantly different crystal structures, and the bromide compound displays variability in its metal–ligand distances.

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[5,10,15,20-Tetra­kis(3-cyano­phen­yl)porphyrinato]copper(II) exhibits a C2h-symmetric ααββ conformation, despite an unsymmetrical crystal environment, and is situated on a crystallographic centre of symmetry. The CuII ion adopts a genuine square-planar coordination by the four pyrrole N atoms.

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The C—H⋯N inter­actions in three polymorphs of 5,6-dimethyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)meth­yl]-1H-benzimidazole are compared. Inter­action energies for pairs of mol­ecules are calculated using density functional theory.

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The crystal structures of the benzoate, carbonate and thio­carbonate derivatives of myo-inositol 1,3,5-orthoformate are compared and correlated with their inter­molecular acyl-transfer reactivity. Compounds that showed facile inter­molecular acyl-transfer reactivity showed a favourable orientation of the reactive groups, i.e. electrophile (C=O) to nucleophile (–OH), with the requisite geometry in their crystal structures. In contrast, compounds that did not exhibit inter­molecular acyl-transfer reactions are devoid of reactive geometry.

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The synthesis, crystal structures and Hirshfeld surface analysis of four new organic–inorganic salts are reported. Extensive three-dimensional hydrogen-bonding patterns are formed.

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A two-dimensional CoII coordination polymer exhibits excellent third-order nonlinear absorption and self-focusing effects. The third-order nonlinear optical susceptibility χ(3) is 1.07 × 10−8 esu.

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In the crystal structure of a new MnII complex, obtained using flexible imidazole-containing 1,3,5-tris­[(1H-imidazol-1-yl)meth­yl]benzene (timb) ligands with manganese sulfate through solvothermal reaction, the MnII atom adopts an octa­hedral geometry and adjacent MnII centres are linked by timb ligands to generate a two-dimensional layered structure. The two-dimensional sheets are further connected into a three-dimensional porous network by bridging anionic sulfate ligands.

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The crystal structure of ethyl 4-(9H-carbazol-9-yl)benzoate revealed a surprisingly large number of independent mol­ecules per unit cell and an intricate packing motif.

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Two forms of lamotrigine di­thio­benzoate (i.e. the hydrate and the anhydrous form) have as the main structural motif a hydrogen-bonded tetra­mer made up of three concatenated R_{2}^{2}(8) elemental synthons.

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Two new isostructural zinc(II) complexes based on the 1-[(benzotriazol-1-yl)meth­yl]-1H-imidazole (bmi) ligand exhibit mononuclear structures, in which the bmi ligands coordinate to the central metal ions in a monodentate mode.

Special and virtual issues

Acta Crystallographica Section C is planning special issues on

NMR Crystallography

Scorpionates: a golden anniversary

Full details are available on the special issues page.

The latest virtual issue features Coordination polymers, with an introduction by Len Barbour.

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