Inorganic Chemistry Communications (v.4, #9)

A novel complex {[Mn(bipy)(azpy)2(NCS)2]·H2O} n (where bipy =4,4-bipyridine, azpy = 4,4-azobispyridine) is synthesized and characterized. The molecule structure shows that it is composed of an infinite “rod” with open sidearms. Two-dimensional undulating plane networks with large rhombic channels ca. 21.7×11.6 Å is constructed by the neutral rod via hydrogen-bonding interaction. Three parallel interpenetrating two-dimensional (4,4) networks form a novel infinite triple helices with rhombic channels ca. 19×9 Å.
Keywords: Crystal structure; Triple helices; Interpenetration network; Mn complex;

A complex salt (NMe4)2[Hg(C7H4NS2)4] and eight heterometallics MM(C7H4NS2)4[M=Co(II),Ni(II),Zn(II),2Cu(I) or 2Ag(I);M =Zn(II)  or Hg(II)] have been synthesized and characterized by elemental analyses, molar conductance and magnetic susceptibility measurements, relevant spectroscopy [IR, electronic, EPR, 1H and 13C NMR] and ES+ mass spectrometry. In general, their σ rt ∼10−13   S cm −1 is low, however NiHg(C7H4NS2)4, CoZn(C7H4NS2)4 and Ag2Hg(C7H4NS2)4 show semiconductivity in the 303–523 K range.
Keywords: Heterometallic 2-sulfanylbenzothiazolate complexes; Electrical conductivity; Semiconductivity; Infrared spectroscopy;

The reaction of cobalt nitrate hexahydrate with 4,4-bipyridine (BPY) under hydrothermal conditions produced a new cationic pocket-like coordination polymer built by mixed double-hydrogen-bonded and coordinated 4,4-bipyridine rectangular-grid with inclusion species, and this material has been fabricated into metal–organic nanofibers by electrospinning.
Keywords: Coordination polymer; Cationic structure; Hydrothermal reactions; Electrospinning; Nanofiber; 4,4-Bipyridine;

Unusual complexes formed by the early lanthanides with 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)-pyridines by Michael G.B. Drew; Denis Guillaneux; Michael J. Hudson; Peter B. Iveson; Charles Madic (462-466).
The addition of lanthanide(III) nitrates (La–Sm) to the actinide(III) extracting agents, 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)-pyridines in a 1:1 ratio, results in the crystallisation of unusual dimeric complexes [Ln2(L1)2(NO3)6] as well as more usual mononuclear complexes.
Keywords: Lanthanides; Actinides; Extraction; Nuclear reprocessing;

Hydrothermal synthesis of three new 3-D framework rare-earth mellitates by Stephen S.-Y. Chui; Alvin Siu; Xue Feng; Ze Ying Zhang; Thomas C.W. Mak; Ian D. Williams (467-470).
Hydrothermal reaction of rare-earth ions and mellitic acid [MEL-H6=C6(COOH)6] has been carried out to determine the effects of metal size and ancillary aquation on polymer architecture. Three new 3-D framework rare-earth mellitate polymer types are formed with reduced aquation levels compared to ambient phases. Larger ions Ln=La to Er form 9-coordinate [Ln2(MEL)(H2O)6] 1 (orthorhombic, Pnnm, for La a=13.642(2), b=6.769(1), c=10.321(2) Å, V=953.1  A ̊ 3 ) and smaller ions Ln=Tm to Lu form the 7-coordinate [Ln2(MEL)(H2O)4]H2O 2 (tetragonal, P4/ncc, for Tm a=18.443(3), c=10.374(2) Å, V=3529  A ̊ 3 ). In the case of Ln=Er, Tm a third type with μ-aqua groups is found [Ln2(MEL)(μ-H2O)2(H2O)2] 3 (monoclinic P21/c, for Tm a=5.781(1), b=14.840(1), c=8.920(1) Å, β=93.46(1)°, V=763.8  A ̊ 3 ). This 8-coordinate phase is favored over 1 at higher temperature (200°C) for Er and favored over 2 at lower temperatures (160°C) for Tm.
Keywords: Hydrothermal synthesis; Lanthanides; Coordination polymers; Microporous compounds;

A palladium complex containing a new C2-symmetric bidentate non-racemic oxalamidine ligand: synthesis and catalytic properties by Jairton Dupont; Gunter Ebeling; Marcelo R. Delgado; Crestina S. Consorti; Robert Burrow; David H. Farrar; Alan J. Lough (471-474).
Non-racemic (S,S,S,S)-(-)-2,2-bis-(4,5-diphenyl-1, 3-imidazoline) 1 has been prepared in good yields from the reaction of (S,S)-(-)1,2-diphenylethylenediamine with diethyl oxalimidate. The reaction of 1 with sodium tetrachloropalladate yields [PdCl 2( 1 )] complex 2, whose structure has been ascertained by means of X-ray diffraction analysis. Complex 2 catalyzes the hydro-arylation of norbornene in good catalytic activity but with poor enantioselectivity.
Keywords: Palladium; Catalysis; Amidines; Hydro-arylation; Asymmetric;

Deprotonation of a ruthenium (II) complex incorporating a bipyrazole ligand leading to optical and electrochemical switching by Huw Jones; Mike Newell; Clive Metcalfe; Sharon E. Spey; Harry Adams; Jim A. Thomas (475-477).
The synthesis of a Ru(II) complex incorporating the 3,3′-bipyrazole (bpyz) ligand is reported. Deprotonation of the ligand leads to shifts in both the metal-to-ligand charge transfer (MLCT) band (80 nm) and the RuIII/II oxidation couple (>750  mV ) of the complex.
Keywords: Ruthenium complex; Bipyrazole complex; Crystal structure; Molecular devices;

A pair of racemic (ΔΔ/ΛΛ) μ-[N,N -bis(2-aminoethyl)-1,2-ethanediamine-N1,N1,N2,N2]-bis[N,N -(bis(2-aminoethyl)-1,2-ethanediamine-N,N ,N″,N‴)]dinickel(II) compounds were prepared and structurally characterized by crystallography. The perchlorate salt ( 1 ) crystallizes in the space group Pbcn; while the 4,4-biphenyldisulfonate (BPDS) salt ( 2 ) crystallizes in the chiral space group C2 with a pair of ΔΔ and ΛΛ enantiomers in the unit cell, which represents the first example of kryptoracemic crystallization documented for a binuclear coordination compound. The extensive hydrogen bonds between the SO3 groups of the BPDS anions and the amino hydrogens of the complex cations are accounted for the kryptoracemic crystallization pathway adopted by 2 .
Keywords: Nickle(II); Trien; Dinuclear complex; X-ray crystallography;

A photoluminescent polymeric Cu(I) complex containing a novel fragment [Cu4(bta)3(PPh3)4]+ (btaH=benzotriazole) like a reverse-umbrella has been synthesized and structurally characterized.
Keywords: Copper(I) complex; Benzotriazole; Triphenylphosphine; Photoluminescent;

The first half-sandwich d0-metallacarboranes stabilized by metal–nitrogen sigma bond using C(cage)-appended anionic alkylamido moiety: a synthetic investigation by Yinghuai Zhu; Kamesh Vyakaranam; John A. Maguire; William Quintana; Francesc Teixidor; Clara Viñas; Narayan S. Hosmane (486-489).
The 1:1 molar reaction of the potassium/dilithium triple salt of the [nido-7-(NHCH2)-7,8-C2B9H10]3− trianion with anhydrous MCl4 in dry tetrahydrofuran (THF) at −78°C, followed by extraction with dry benzene and precipitation with n-pentane, resulted in the formation of the corresponding novel half-sandwich d0-metallacarborane, closo-1-M[(Cl)(THF) n ]-2-(1-σ-NHCH2)-2,3-η5-C2B9H10 [M=Zr (3), n=1; Ti (4), n=0] in 57% and 49% yields, respectively.
Keywords: Group-4-metallacarborane; Half-sandwich; C(cage)-alkylamido; Constrained geometry;

The first copper(I) complex of tris(hydroxymethyl)phosphine by D. Saravana Bharathi; M.A. Sridhar; J. Shashidhara Prasad; Ashoka G. Samuelson (490-492).
The first copper(I) complex of tris(hydroxymethyl)phosphine (THP) has been synthesized from a reaction with [Cu(CH3CN)4]ClO4. The crystal structure and spectroscopic properties of this complex showing the tetrahedral coordination around copper and a deprotonated THP coordinated to Cu through P are presented.
Keywords: Tris(hydroxymethyl)phosphine; Copper(I) complex; Water soluble; X-ray structure;

Thermally stable magnesium-free layer structure birnessite (OL-1) has been synthesized and modified in the presence of other metal cations used as framework dopants by the air oxidation of Mn (II).
Keywords: Octahedral molecular sieves; Framework substitution; Porous materials;

The first metal complex containing a silylated β-diketonate ligand: bis(2,2,6,6-tetramethyl-2-sila-3,5-heptanedionato) copper(II) by Kulbinder K. Banger; Andrei Kornilov; Rolf U. Claessen; Eric T. Eisenbraun; Alain E. Kaloyeros; Paul J. Toscano; John T. Welch (496-500).
A facile preparation of 2,2,6,6-tetramethyl-2-sila-3,5-heptanedione (tmshdH), exemplar of a new class of ligands, the sila-β-diketones, has been developed. Silicon substitution in the ligands has profound effects on the volatility, thermal properties, crystal packing, and electronic spectrum of the homoleptic Cu(II) complex, Cu(tmshd)2.
Keywords: Sila-β-diketone; Copper complex; UV/Vis spectroscopy; Chemical vapor deposition; Volatile complexes; Crystal structure;

Synthesis and crystal structure of a one-dimensional coordination polymer of nickel(II) with 4-(imidazol-1-ylmethyl)benzoate anion by Jian Fan; Yan-An Zhang; Taka-aki Okamura; Zhi-Hong Zou; Norikazu Ueyama; Wei-Yin Sun (501-503).
A one-dimensional (1D) coordination polymer, [NiII(imbz)2(H2O)2] n 1 [imbz=4-(imidazol-1-ylmethyl)benzoate anion] was synthesized by treatment of Ni(CH3COO)2·4H2O with piperidinium salt of 4-(imidazol-1-ylmethyl)benzoic acid 2, and characterized by X-ray crystallography. The thermogravimetric analysis (TGA) and magnetic property of the compound 1 are also reported.
Keywords: Crystal structure; Nickel(II) complex; 1D coordination polymer; Magnetic property;

A three-dimensional framework of dimeric copper(II) acetate linked by coordinated sodium cations by Chuan-De Wu; Can-Zhong Lu; Wen-Bin Yang; Hong-Hui Zhuang; Jin-Shun Huang (504-506).
The reaction of a DMSO solution of Cu(OCOCH3)2·H2O with CH3COONa·3H2O in the presence of acetate acid gives the formation of sodium cations linking six-coordinated copper(II) acetates into microporous network structure, NaHCu2(OCOCH3)6 1. The powder ESR of 1 reveals that there might exist exchange interactions between these copper(II) cations.Graphic
Keywords: Dimeric copper(II) acetate; ESR spectrum; Network structure; Trans-influence effects;

Electrical transport properties of a supramolecular assembly by Arvind Pan; Aswini Ghosh; Shubhamoy Chowdhury; Dipankar Datta (507-510).
The direct current conductivity of the urea–[CuIL2]PF6 supramolecular assembly (1) has been measured in the temperature range 24–118°C. It is found that 1 behaves as a semiconductor in 24–33°C, as a metal in 33–63°C and again as a semiconductor in 63–118°C. Such transitions between semiconductor and metal like behaviour have not been observed earlier in the clathrates.
Keywords: Clathrates; Supramolecule; Electrical conductivity; Copper(I) complexes; Urea;

A single-molecular magnet: [Mn12O12(O2CCH2Br)16(H2O)4] by Hui-Lien Tsai; Da-Min Chen; Chen-I Yang; Tyn-Yih Jwo; Ching-Shuei Wur; Gene-Hsiang Lee; Yu Wang (511-514).
The synthesis, X-ray crystal structure and magnetic properties of a new dodecanuclear manganese complex [Mn 12 O 12(O 2 CCH 2 Br)16(H 2 O)4]   ·   4CH 2 Cl 2( 2 ) · 4CH 2 Cl 2 are reported. Complex 2  · 4CH 2 Cl 2 crystallizes in tetragonal space group I41/a with the following cell dimensions at 293(2) K: a=b=26.697(4) Å, c=13.246(4) Å, and Z=4. The results of DC and AC magnetic susceptibility studies are described. DC measurements show the presence of hysteresis loops, and the out-of-phase component of AC magnetic susceptibilities has a frequency dependent maximum. Step-like features are seen on hysteresis loops and quantum mechanical tunneling could be the origin of these unusual relaxations.
Keywords: Crystal structure; Single-molecule magnet; Step-like hysteresis loop; Magnetic quantum tunneling;

Two half-sandwich indenyl zirconium complexes [η5: η 1 -C 9 H 6 -1-C(R 1)(R 2)-o-C 6 H 4–OMe]ZrCl 3·THF  (R 1=R 2=Me  ( 1 );R 1=Me,R 2=Et  ( 2 )) were synthesized successfully from the reaction of trimethylsilyl complexes of the ligands with ZrCl4. The X-ray structures of them were also determined. In spite of the existence of two stereogenic elements, complex 2 was isolated as a single pair of enantiomers ((pR,S) and (pS,R)). And besides the coordinated THF molecule in the crystal structure of complex 2, there is an additional THF molecule in the cell, which hardly has interaction with other atoms.
Keywords: Half-sandwich zirconium complex; Substituted indenyl; Diastereoisomer; Coordination;

Synthesis of {1,3-bis(η5-tetramethylcyclopentadienyl)-1,1,3,3-tetramethyldisiloxane}dichlorotitanium(IV) via hydrolysis of bis{η5-(N,N-dimethylaminodimethylsilyl)tetramethylcyclopentadienyl}dichlorotitanium(IV) by Jaroslav Zemánek; Michal Horáček; Ulf Thewalt; Petr Štěpnička; Jiřı́ Kubišta; Jiřı́ Čejka; Lidmila Petrusová; Karel Mach (520-525).
Bis{η5-(N,N-dimethylaminodimethylsilyl)tetramethylcyclopentadienyl}dichlorotitanium(IV), [TiCl25-C5Me4(SiMe2NMe2)}2] (1), easily undergoes hydrolytic cleavage of the Si–N bonds to give dimethylamine and {1,3-bis(η5-tetramethylcyclopentadienyl)-1,1,3,3-tetramethyldisiloxane}dichlorotitanium(IV), ansa-[TiCl2{(η5-C5Me4SiMe2)2O}] (2), in almost quantitative yields. The crystal structures of compounds 1 and 2 were determined by single-crystal X-ray diffraction.
Keywords: Titanium; Titanocenes; Pendant amine group; Hydrolysis; Siloxane bridge; Crystal structure;