Inorganic Chemistry Communications (v.4, #6)

Contents (iii-iv).

Cis addition of dimethylamine to the coordinated nitriles of cis- and trans-[PtCl2(NCMe)2]. X-ray structure of the amidine complex cis-[PtCl2{E-N(H)C(NMe2)Me}2]·CH2Cl2 by Rino A. Michelin; Roberta Bertani; Mirto Mozzon; Alessandro Sassi; Franco Benetollo; Gabriella Bombieri; Armando J.L. Pombeiro (275-280).
The reaction of cis-[PtCl2(NCMe)2] with a 5-fold excess of Me2NH in CH2Cl2 at −10°C affords in high yield the bis-amidine complex cis-[PtCl2{E-N(H)C(NMe2)Me}2] (E,E-2), where both the amidine ligands assume the E configuration. E,E-2 was characterized by X-ray structure analysis, NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). The corresponding reactions of trans-[PtCl2(NCMe)2] with Me2NH gave the bis-amidine complex trans-[PtCl2{E-N(H)C(NMe2)Me}2] (E,E-3) and the mono-amidine derivative trans-[PtCl2{E-N(H)C(NMe2)Me}(NCMe)] (E-4).
Keywords: Platinum complexes; Nitrile complexes; Amidine complexes; X-ray structure;

Catalytic activity of dicationic platinum(II) and rhodium(II) complexes towards 9-diazofluorene by Roberta Bertani; Rino A. Michelin; Mirto Mozzon; Alessandro Sassi; Marino Basato; Andrea Biffis; Gianluca Martinati; Marco Zecca (281-284).
9-Diazofluorene (DAF) is catalytically decomposed at 25°C in CH2Cl2 in the presence of 1 mol% of the dicationic platinum(II) complex cis-[Pt(PPh3)2(CH3CN)2][BF4]2 (1) to give the olefin product 9,9-bifluorenylidene in high yield. Furthermore, DAF undergoes an insertion reaction into the O–H bond of methanol at 25°C in CH2Cl2/MeOH (DAF/MeOH molar ratio 1/20) in the presence of 1 mol% of 1 to give 9-methoxyfluorene in excellent yield. With neutral or cationic dirhodium(II) complexes as catalysts the same reaction yields further products, suggesting the existence of different parallel reaction pathways.
Keywords: Platinum complexes; Rhodium complexes; Diazo compounds; Carbenes; Insertion reactions;

A new binuclear complex with mixed-ligands {(ox)(H2O)OMo(μ-O)2MoO(H2O)(bipy)}·2H2O was obtained from an aqueous reaction of Na2MoO4·2H2O with Nd 2 O 3,  H 2 C 2 O 4 ,  2,2-bipy, and characterized by single-crystal X-ray diffraction and spectroscopic methods. Crystal data: C 12 H 16 Mo 2 N 2 O 12, M=572.15, monoclinic, P2(1)/c, a=6.8400(10), b=11.6033(2), c=22.9006(4) Å, β=95.8590(10)°, V=1808.05(5) Å3, and Z=4,  μ(Mo-Kα)=1.455  mm −1 . The crystal structure consists of neutral binuclear molybdenum {(ox)(H2O)OMo(μ-O)2MoO(H2O)(bipy)} units and crystallization water molecules, which were held together to an extensive three-dimensional network via several interactions such as conventional OH⋯O, aromatic CH⋯OCO hydrogen bonds, π–π stacking interactions between parallel aromatic bipy rings and face-to-face stacking interactions between parallel oxalate groups.
Keywords: Crystal structure; Binuclear molybdenum compound; Hydrogen bonds; Stacking interactions;

Interaction of Rh(I) with a new polydentate O4,N-donor pyrazolone able to form mononuclear, dinuclear and heterobimetallic compounds by Claudio Pettinari; Fabio Marchetti; Andrei Drozdov; Vyacheslav Vertlib; Sergei Troyanov (290-293).
Reaction of the new polydentate O4,N-donor ligand, namely 2,6-bis[4(1-N-phenyl-3-methyl-pyrazolium-5-one)carbonyl]pyridinium trichloride [H5QN]Cl3, with [Rh(COD)Cl]2 affords the dinuclear compound [Rh2(COD)2([H3QN]Cl3)] 1 which reacts with PPh3 forming [Rh(PPh3)2Cl2(HQN)] 2, able to interact with SnMe2Br2 yielding the heterobimetallic adduct [Rh(PPh3)2 Cl2(HQN)SnMe2Br2] 3; the X-ray structure of 2 shows the Rh(III) center in a slightly distorted octahedral environment with Cl atoms situated in cis-position and two phosphine groups in trans.
Keywords: Rhodium complexes; Oxidative addition; Acylpyrazolones; X-ray crystal structure; Heterobimetallic complexes;

A simple direct preparation of nanocrystalline γ-Mn2O3 at ambient temperature by Zhou Gui; Rong Fan; Xian-Hui Chen; Yi-Cheng. Wu (294-296).
Nanocrystalline γ-Mn2O3 has been prepared directly by the reduction of aqueous KMnO4 with hydrazine solution at ambient temperature, without post-treatment of heating. X-ray powder diffraction (XRD) pattern demonstrates its good phase purity. Transmission electron microscopy (TEM) images show homogeneous nanoparticles with a narrow size distribution. The average grain size is about 9 nm. The evolution of crystallite size upon the annealing temperature was investigated. The effect of various reaction factors, e.g., pH, concentration of N2H4 and additants, on the nature of products was also investigated.
Keywords: Synthesis; γ-Mn2O3; Nanocrystalline; Microstructure;

A three-dimensional cobalt(II)-coordination polymer based on 3,5-pyridinedicarboxylate by Dongwon Min; Seung Soo Yoon; Ji Hwa Lee; Myungkoo Suh; Soon W. Lee (297-300).
Hydrothermal reaction between cobalt(II) nitrate and 3,5-pyridinedicarboxylic acid in the presence of NaOAc and NaCl gave a 3-D cobalt(II)-coordination polymer, Co(3,5-pyridinedicarboxylato)(H2O) (1). X-ray structure determination showed that compound 1 has a 3-D infinite network based on cobalt–carboxylate building blocks.
Keywords: Cobalt(II) nitrate; 3,5-pyridinedicarboxylic acid; 3-D cobalt(II)-coordination polymer;

Highly stable open frameworks of Ln–Cu (Ln=La, Ce) 3D coordination polymers containing spacious hexagon channels and unusual μ2-H2O bridges by Qin-De Liu; Jun-Ran Li; Song Gao; Bao-Qing Ma; Fu-Hui Liao; Qing-Zhong Zhou; Kai-Bei Yu (301-304).
Novel 3D Ln–Cu heteronuclear complexes [Ln2Cu32-H2O)(DGA)6(H2O)3]·3H2O (Ln = La, Ce) containing unusual μ2-H2O bridges were formed by linking mononuclear units of [Ln(DGA)3] (H2DGA = diglycolic acid) by copper ions, to produce an open framework containing large amount of spacious hexagon channels with stable skeletons as demonstrated by thermogravimetric analysis (TGA) and X-ray diffraction (XRD) analysis.
Keywords: Heteronuclear; Coordination polymer; Open framework; Hydrogen bond;

An alternating linear chain of nickel(II) ions and azide has been prepared in a controlled fashion from dinuclear building blocks, in which an end-to-end binding mode of the azido ligand is predetermined by the compartmental dinucleating pyrazolate scaffold. The structure and unexpected magnetic properties of the coordination polymer are reported.
Keywords: Nickel; Azide; N-ligands; Magnetic properties; Chain compounds;

The dinuclear complexes (arene)2Ru2Cl4 (arene=benzene, p-cymene, durene, hexamethylbenzene) react in aqueous solution to give, in addition to the known cationic trichloro complexes [(arene)2Ru2(μ-Cl)3]+, the new dichloro hydroxo cations [(arene)2Ru2(μ-Cl)2(μ-OH)]+ which can be isolated as the perrhenate salts.

The octahedral Ni(II) complex with dioxo-2,6-pyridinediylbis(ethylidyne-1-hydrazinyl-2-ylidene)diacetic acid (H2dapoamh) was synthesized and X-ray analysis confirmed the tridentate coordination for the neutral ligand. Besides, the square planar Ni(II) complex with dianion 2,2-(2,6-pyridinediyldiethylidyne)dioxamohydrazide (H2dapsox) was synthesized and characterized.
Keywords: Ni(II) complexes; 2,6-diacetylpyridine derivative; Octahedral and square-planar complexes; X-ray crystal structure;

A novel maze-type network assembled by copper(II) and 2,2-dicarboxydiphenylthioether: [(Cu4(C5H5N)8{S(C6H4CO2)2}4(H2O)2]·2H2O) n by R.K. Bhubon Singh; K.M. Abdul Malik; S. Ozra Ghodsi Mahalli; Mohamed Salah El Fallah; N.K. Karan; Samiran Mitra (315-318).
A novel polymeric copper(II) complex ([Cu4(C5H5N)8{S(C6H4CO2)2}4(H2O)2]·2H2O) n assembled by 2,2-dicarboxydiphenylthioether and pyridine and bridged by carboxylato groups has been synthesised and structurally characterised by single crystal X-ray structural studies. The maze-type structure contains one tetranuclear 40- and one dinuclear 8-membered metallocycles, both of which are centrosymmetric and form the repeat unit in the polymer chain.
Keywords: Metallomacrocyclic; 2,2-Dicarboxydiphenylthioether; Tetranuclear copper(II); Pyridine; Crystal structure;

Refutation of an alleged example of a disordered but centrosymmetric triboluminescent crystal by F. Albert Cotton; Lee M. Daniels; Penglin Huang (319-321).
The crystal structure of triboluminescent triethylammonium tetrakis(dibenzoylmethide)-europium has been reinvestigated with the result that crystals previously assigned to the centric space group I2/a actually belong to the non-centric space group Ia.
Keywords: Triboluminescence; Europium complex; Crystal structure;

Structure and magnetic properties of ferrimagnetic chain formed by manganese(II) and nitronyl nitroxides by Zhi-Liang Liu; Qi-Hua Zhao; Su-Qi Li; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan (322-325).
We report the structure of a one-dimensional chain compound formed by manganese(II) hexafluoroacetylacetonate (hfac) and nitroxide radical 2-diethylin-4,4,5,5-tetramethyl-4,5-dihydro-1-imidazol-1-oxy-3-oxide (NITPhNEt2), Mn(hfac)2·NITPhNEt2·C2H5OH, which crystallize in the monoclinic C2/c space group with a=28.4028(2) Å, b=13.4494(8) Å, c=23.8493(1) Å, β=124.4110(1)°, and Z=8. In the compound Mn(hfac)2 units are bridged by the MITPhNEt2 radical which is cis-coordinated toward the manganese originating a chain. The magnetic susceptibility in the range of temperature 4–300 K is typical of a ferrimagnetic chain formed by alternating spins 5/2 and spins 1/2.
Keywords: Nitronyl nitroxide radical; Complex; One-dimensional chain; Ferrimagnetic;