Volume 37, Issue 5-6

The reaction between i Pr 2 PCl and one equivalent of MeMgBr, followed by one equivalent of BH 3 ·SMe 2 , gives the phosphine-borane i Pr 2 P(BH 3 )Me ( 4 ). Treatment of 4 with n BuLi, followed by Me 3 SiCl, gives the sterically demanding phosphine-borane { i Pr 2 P(BH 3 )}(Me 3 Si)CH 2 ( 5 ) in good yield. Metalation of 5 with n BuLi yields { i Pr 2 P(BH 3 )}(Me 3 Si)CHLi ( 6 ), which was crystallised as the TMEDA adduct [{ i Pr 2 P(BH 3 )}(Me 3 Si)CH]Li(TMEDA) ( 6a ) and characterised by X-ray crystallography [TMEDA = N,N,N′,N′ -tetramethylethylenediamine]. The reaction between two equivalents of in situ -generated 6 and Cp 2 Sn in toluene gives the dialkylstannylene [{ i Pr 2 P(BH 3 )}(Me 3 Si)CH] 2 Sn ( 7 ), which was crystallised from methylcyclohexane/THF as the rac diastereomer. X-ray crystallography reveals that stabilisation of the Sn centre in 7 is afforded by two agostic-type B-H…Sn interactions, one from each BH 3 group.

The reaction of [FeCp*(CO) 2 ] 2 in CH 2 Cl 2 with BiBr 3 in a 1:1 molar ratio gave the novel bismuth compound [Bi 6 Cp* 6 Br 9 ][Bi 7 Br 24 ] ( 1 ), which is composed of a cationic and an anionic bismuth bromido cluster: the cation is based on a hexanuclear bismuth {Bi 6 }-octahedron and the anion showing the first heptanuclear bismuth-bromido cluster within the class of bromido bismuthates.

The self-assembly of [Zn(L)(H 2 O) 2 ]·Cl 2 and 1,2-cyclopentanedicarboxylic acid generates a 2D hydrogen-bonded polymer [Zn(L)(Hcpdc)] (L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0 1.18 0 7.12 ]docosane, H 2 cpdc= 1,2-cyclopentanedicarboxylic acid) ( 1 ). Complex 1 is characterized by X-ray crystallography, spectroscopy, and thermogravimetric analyzer. The crystal structure of 1 shows a distorted octahedral coordination geometry around the zinc (II) ion, with the four secondary amines of the macrocycle and two carboxylate oxygen atoms of the Hcpdc - ligand in the trans position. The compound crystallizes in the monoclinic system P 2 1 /c with a =8.6002(10), b =10.4906(11), c =19.008(2) Å, β (°)=92.949(7)°, V =1712.6(3) Å 3 , Z =2. The IR spectrum and TGA behavior of the compound are significantly affected by the Hcpdc - ligand.

We describe a convenient and useful procedure for the synthesis of various 2,5-dimethyl-N-substituted pyrrole derivatives by the addition of 2,5-hexadione with aromatic amines, heteroaromatic amines and aliphatic amines catalyzed by MgI 2 etherate (MgI 2 ·(OEt 2 ) n ) in good to excellent yields.

Complexes of Co(II), Ni(II), Cu(II), and Zn(II) containing N 2 S 2 ligand have been synthesized from the template condensation reaction between 1,2-ethanedithiol, o -bromoaniline and dimethyl tin dichloride in 1:2:1 molar ratio. It resulted in the formation of new series of 11-membered N 2 S 2 -Tin macrocyclic complexes [MLX 2 Sn(CH 3 ) 2 ] (M=Co(II) or Zn(II); X=Cl or NO 3 ); and [MLSn(CH 3 ) 2 ]X 2 (M=Ni(II) or Cu(II); X=Cl or NO 3 ). The complexes were characterized using techniques including elemental analyses, IR, 1 H NMR, 119 Sn NMR, EPR, electronic spectral studies, conductivity, and magnetic susceptibility measurements. The reducing power of the Co(II) and Cu(II) complexes have been checked and compared. The complexes derived from nickel and copper have been found to show square-planar geometry, while octahedral geometry is projected for the cobalt and zinc complexes.

Two bis(triorganotin) 2,6-pyridinedicarboxylates, 2,6-C 5 H 3 N(COOSnR 3 ) 2 (R=C 6 H 11 - c , 1 ; C 6 H 5 C(CH 3 ) 2 CH 2 , 2 ), have been synthesized by the reaction of 2,6-pyridinedicarboxylic acid with triorganotin hydroxide in toluene-ethanol and characterized by means of elemental analysis, FT-IR, 1 H NMR spectroscopy, and single crystal X-ray diffraction analysis. In the compounds, a 2,6-pyridinedicarboxylate dianion binds two triorganotin units in a monodentate manner and both tin atoms exist in a distorted tetrahedral environment. Bioassay results have shown that the compounds possess good in vitro cytotoxic activity against two human tumor cell lines, Hela and MCF-7.

The specific reactivity of the tetraradicaloid derivative spirobis(pentagerma[1.1.1]propellane) toward the halogenating reagents (CCl 4 and I 2 ) is reported.

Monoclinic 2,6-Mes 2 C 6 H 3 SiF 3 comprises two crystallographically independent molecules in the asymmetric unit, which are associated by a weak Si···F contact. The previously known orthorhombic modification lacks this structural feature.

The title compound bis( m -terphenyl)zinc (2,6-Mes 2 C 6 H 3 ) 2 Zn was obtained by the metathesis reaction of the lithium organyl 2,6-Mes 2 C 6 H 3 Li with zinc difluoride ZnF 2 and fully characterised by X-ray crystallography.

The title compounds [(8-Me 2 NC 10 H 6 ) 2 TeX] 2 TeX 6 ( 1 , X=Cl; 2 , X=Br) were obtained by the oxidation of (8-Me 2 NC 10 H 6 ) 2 Te with SO 2 Cl 2 and Br 2 and the subsequent addition of TeCl 4 and TeBr 4 , respectively, and were characterized by X-ray crystallography and multinuclear NMR spectroscopy. Due to the intramolecularly coordinating 8-dimethylaminonaphthyl substituents, 1 and 2 comprise loosely associated ion pairs of distorted trigonal bipyramidal [(8-Me 2 NC 10 H 6 ) 2 TeX] + cations and octahedral TeX62-${\rm{TeX}}_{\rm{6}}^{{\rm{2 - }}}$ anions (X=Cl, Br).

Reported here are the syntheses and molecular structures of three novel arylindium phosphinates, [(2,6- Mes 2 C 6 H 3 In) 2 (OH) 2 (O 2 PMe 2 ) 2 ] ( 1 ), [(2,6-Mes 2 C 6 H 3 In) 2 (OH)(O 2 PPh 2 ) 3 ] ( 2 ), and [(2,6-Mes 2 C 6 H 3 In)(O 2 PMe 5 C 3 H) 2 (H 2 O) 2 ] ( 3 ), which were obtained by condensation reaction of the m -terphenylindium dihydroxide [(2,6-Mes 2 C 6 H 3 In(OH) 2 ] 4 with dimethylphosphinic acid, diphenylphosphinic acid, and 2,2,3,4,4-pentamethylphosphetanic acid, respectively.

A few crystals of the title compound Te 2 Mg 2 (μ 3 -Cl 2 )(μ 2 -Cl 4 )Cl 6 (THF) 4 · CH 2 Cl 2 ( 1· CH 2 Cl 2 ) were isolated accidentally from a reaction mixture that contained the starting materials TeCl 4 and t -BuMgCl in THF and that was recrystallized from CH 2 Cl 2 . The molecular structure of 1· CH 2 Cl 2 determined by X-ray crystallography features a rare TeCl 3 - moiety.