Volume 32, Issue 12

The partial hydrolysis of AsPh 4 [MoNCl 4 ] (AsPh 4 = [(C 6 H 5 ) 4 As]) leads to AsPh 4 [MoOCl 4 ]. Both salts crystallize isotypic in the tetragonal space group P 4/n with Z = 2. The crystal structures are built up by AsPh 4 cations and square pyramidal [MoXCl 4 ] anions with the symmetry C 4v . The Mo—N distance of 166 pm and the slightly longer Mo-O distance of 171 pm indicate strong π-bonding.

In the systems K-Al, Ga, In-Si, Ge, Sn each phase of composition K 8 (3B, 4B) 46 was prepared. The crystal structure for K 8 (Al, Ge) 48 and K 8 (Ga, Ge) 46 was determined by X-ray investigations. In the systems Na-Al, Ga-Si, Ge the compounds Na 8 (Al, Ge) 46 (crystal structure determined), Na 8 (Ga, Si) 46 and Na 8 (Ga, Ge) 46 were prepared.

The new intermetallic compound Sr 3 As 4 has been prepared and structurally characterized by X-ray single crystal methods. Sr 3 As 4 crystallizes orthorhombic with a = 1484 ± 2 pm, b = 1789 ± 2 pm, c = 597 ± 1 pm, space group Fdd2. Remarkable element of the structure are As 4 -chains.

The ternary borides MgNi 2,5 B 2 and Li 1,2 Ni 2,5 B 2 have been prepared and investigated by X-ray methods. They are isotypic and crystallize hexagonal in the space group P6 2 22—D 4 6 -with the following constants : MgNi 2 .5B 2 α = 4.887 ± 0.002 Å, c = 8.789 ± 0.004 Å; Li 1.2 Ni 2.5 B 2 a = 4.842 ± 0.002 Å, c = 8.664 ± 0.004 A. The structure contains boron-pairs and can be derived from the CeCo 3 B 2 -type of structure.

The title compound, C 16 H 18 N 3 S · Is, crystallizes in the monoclinic space group P 2 1 /a with a = 11.32(2) Å, b = 16.59(1) A, c = 11.52(2) Å, β = 109.56(8). The structure was solved by Patterson and Fourier methods and refined by least squares to R = 0.066, based on 1042 observed intensities. The planar organic cations form regular stacks along c with interplanar distances of 3.46 Å. The stacks are enclosed by slightly asymetric triiodide anions, which form ribbons perpendicular to the cation stacks.

From acidified sodium tungstate solutions mixtures of polytungstates are precipitated by addition of tetraphenylphosphonium ions. By separation with selective organic solvents five different polytungstates were obtained two of them represent a novel polyanion type. Their base to acid ratio is 2:11 respectively 1:6. The other three compounds were identified analytically and by their vibrational spectra as hexatungstate, [P(C 6 H 5 ) 4 ] 2 W 6 O 19 , as decatungstate, [P(C 6 H 5 ) 4 ] 4 Wio 32 , as well as dodecatungstate, [P(C 6 H 5 ) 4 ] 5 H 3 W 12 O 40 , with “Keggin-structure”. The preparation of these compounds is reported and their IR, Raman and UV spectra are discussed.

The isocyanates of silicon (CH 3 ) 2 Si(NCO) 2 and Si(NCO)4 react with CH 3 N[Sn(CH 3 ) 3 ] 2 and N[Sn(CH 3 ) 3 ] 3 to yield the cyclic derivatives 2a-2b as well as the spiro compound 3. The structures of the compounds are discussed on the basis of 1 H NMR and IR data. Mass spectra are not conclusive for assigning a certain structure. SO 2 (NCO) 2 and (CH 3 ) 3 Si-S-Si(CH 3 ) 3 form a cyclic compound 4 which contains two sulfur atoms of coordination number two and four. The results of the mass spectra can be interpreted by assuming that a rearrangement occurred. 4 hydrolyses under formation of 5.

Perhydrolysis of the trimethyl ester of boric acid with Η 2 O 2 /Η 2 Ο (85:15 by weight) in butanolic solvents in the presence of lithium- or cesium-tert-butylate in certain molar ratios yields Li 2 [B 2 (O 2 ) 2 (OH) 4 or Cs 2 [B 2 (O 2 ) 2 (OH) 4 ]. In methanol in the presence of MX 2 , where M = Ca, Sr or Ba and X = N-methylacetamide depending on the experimental conditions M[B 2 (O 2 ) 2 (OH) 4 ] · n CH 3 OH, M[B 2 (O 2 ) 2 (OH) 2 (OOH) 2 ] · CH 3 OH or a compound with a chain structure (anion C) are obtained. Perhydrolysis with H 2 O 2 / H 2 O (98:2 by weight) yields Sr[B 2 (O 2 ) 2 (OOH) 4 ] · CH 3 OH, Ba[B 2 (O 2 ) 2 (OOH) 4 ] · CH 3 OH or Ba[B 2 (O 2 ) 2 (OOH) 4 ] · 2 H 2 O 2 . Based on IR spectra and Raman spectra the structural features of these salts are discussed.

Organoboration, Alkynylstannanes, cis-Diborylalkenes, NMR Trialkylboranes and 2-phenylborolane are reported to add to monoalkynylstannanes under mild reaction conditions. The structures of the organoboration products are discussed by means of 1 H, 11 B, 13 C and 119 Sn NMR spectroscopy. The reaction of the products with boronhalides yields cis-diborylalkenes.

The condensation of phenyldihydroxyborane with pentane-1,5-diols yields no 1,3,2-dioxabora-cyclooctanes but oligomeric boron heterocycles. Their formation can be explained by an exchange of ligands of the boron atom, a process analogous to metathetic ring-opening polymerisation.

The crystal and molecular structures of N-bromobenzamide (NBB), N-bromosuccinimide (NBS), and N,N-dibromobenzenesulfonamide (NBBS) were determined by X-ray structure analysis. The nitrogen atoms in NBB and NBS have a trigonal planar coordination (sp 2 ) and the N—Br distances lie in the same range (1.82 A, 1.84 A). The N—Br distance in NBBS, where the nitrogen atom is sp 3 -hybridized, is somewhat longer (1.88 A). In these structures the molecules are connected by O···H—N (NBB), O···Br—N (NBS) or N···Br—N (NBBS) intermolecular bonds forming endless chains; positivated hydrogen atoms or, in case that they are absent, positivated bromine atoms act as electron acceptors with oxygen or sp 3- hybridized nitrogen atoms. These results suggest, that in solid nitrogen tribromide, the crystal structure of which cannot be determined, the nitrogen atoms will be sp 3 -hybridized and intermolecular contacts via N—Br···N will occur.

Transition metal(II) fluoroborates and nitrates give various complexes with 1,2,4-triazole. Most of these complexes are expected to be polynuclear. The infrared and ligand field spectra have been used to predict some structural aspects of the compounds. The iron complex shows a low spin → high spin transition on heating.

The Mössbauer parameters of (CO) 4 FeL complexes were determined, were L are carbon ligands. The isomer shifts show strong π-interactions, if backbonding from the substituenta of the carbon atom is possible. The quadrupole splitting of [(CO) 4 FeCONMe 2 ] 2 Ni indicates a coordination number of six for the iron atoms with iron-nickel interactions.

C 6 H 5 O-(S)P(N(CH 3 )-NH 2 ) 2 reacts with C 6 H 5 O(S)PCl 2 to give the title compound. The cis- and trans-isomers of this product have been separated and are characterized by their IR, 1 H NMR and 31 P NMR spectra.

The preparation and spectroscopic characterization of osmium tetra(p-tolyl)porphyrin complexes, Os(TTP)LL′ (2c-21; L or L′ = CO, N 2 , EtOH, THF, Py, PPh 3 , P(OMe) 3 , methoxide or oxide) are described. 2c-21 are compared with the analogous octaethylporphyrin complexes, 1c-11. In 2c-21, the porphyrin ligand is a stronger π-acceptor than in 1c-11. The π-acceptor capacity of the porphyrin ligand renders the dinitrogenosmium(II) porphyrins 1j or 2j less stable than the dinitrogenpentammineosmium(II) cation.

The azidophosphine complexes cis-Mo(CO) 4 (R 2 PN 3 ) 2 (R = Me, Ph) may be obtained by nucleophilic displacement reactions of chlorine by azide ion in complexes cis-Mo(CO) 4 (R 2 PCl) 2 . The thermal decomposition and Staudinger reactions were studied. Silylation of NH- or NH 2 -functional groups in aminophosphine and hydrazinophosphine complexes with Me 3 SiCl, Me 2 SiCl 2 or Me 2 SiCl-SiClMe 2 leads to a series of monodentate or bidentate silylaminophosphine complexes, e.g. (CO) 4 Mo(R 2 PNHSiMe 3 ) 2 , (CO) 4 Mo-(R 2 PNH) 2 SiMe 2 , (CO) 4 Mo(R 2 PNH) 2 (SiMe 2 ) 2 , (CO) 4 Mo[R 2 PN(SiMe 3 )(SiMe 3 )NPR 2 ] or (CO) 4 Mo[R 2 P-N(SiMe 3 )SiMe 2 -SiMe 2 -N(SiMe 3 )PR 2 ]. The structures of these complexes are discussed on the basis of their IR and NMR spectra.

Acrylic acid copolymers with styrene, acryloylchloride, acryloylpyrrolidinone, acryloyloxypyridine, acryloylsuccinimid and acryloyltriazole are prepared and coupled with insulin. Metal complexes with BaCl 2 , Cu(CH 3 COO) 2 , La(NO 3 )2, Pb(NO 3 )2 and Hg(NO 3 )2 of the acrylic acid acryloylpyrrolidinone and of the acrylic acid acryloylsuccinimid copolymer are formed and characterized.

Unsaturated compounds are very rapidly hydrogenated with nickel-boride catalyst P-2-Ni without solvent under mild conditions (70-85 °C and 10 bar). Turnover numbers UZ up to 90,000 and space-time-yields of 7440 mmol product per 1 and 1 mgA Nickel in one hour with a mean catalyst activity ā = 124 were observed. This hydrogenation catalyst has a power, which is in the same magnitude of very active noble metal catalysts.

The electric dipole moments of some styrene and trans- and cis-stilbene oxides have been measured, in benzene. From these data some bond angles have been calculated and it has been deduced that in the styrene derivatives the phenyl group is in rapid interconversion about the bond with the triatomic ring.

A high yielding synthesis of naphthazarin or naphthopurpurin can be achieved by SnCl 2 reduction of 2,3-dichloronaphthazarin followed by oxidation in the absence or presence of KO 2 . The spectral properties of these compounds are discussed.

The oxidation of diosgenin (1), cholesterol (2), lanosterol (8), β-sitosterol (4) and stigmasterol (5) with pyridinium chlorochromate furnished the corresponding conjugated and unconjugated ketones i.e., Δ 5(6) -3-one and Δ 4(5) )-3-one. In the case of diosgenin (1), besides the formation of the ketones, regioselective opening of the ring F has also been observed.

Whereas the 5-aminopyrazole derivatives (1 a, b) react with ethyl β-amino-β-trichloro-methylmethylenecyanoacetate (2) in basic media to yield the corresponding 5-aminopyrazolo[1,5-a]pyrimidine derivatives (3a, b), the reaction of la, b with 2 in refluxing acetic acid has afforded oxazino[4,5:5,6]pyrazolo[1,5-a]pyrimidine derivatives. 5-Amino-3-phenyl-4-phenylazopyrazole (12) reacted with 2 in refluxing pyridine to yield the 5-amino-2-phenyl-3-phenylazopyrazolo[1,5-a]pyrimidine derivative (18). On the other hand, the reaction of 12 and 2 in refluxing acetic acid has afforded a mixture of the oxazino[4,5:5′,6′]pyrazolo[1,5-a]pyrimidine derivatives (14) and the pyrazolo[3,4-d]-astriazine derivatives (15). The mechanism of the formation of reaction products is discussed.

Fluorosilylhydrazines react with butyllithium under substitution or cyclisation. A fivemembered heterocyclus is obtained by the intramolecular reaction of N-tert-butyl-aminodimethylsilyl - N′ - fluorodimethylsilyl-N-phenyl-N′-trimethylsilylhydrazine with butyllithium.

MoNCl 3 is prepared by the reaction of Mo(CO) 6 with NCl 3 in CCl 4 -solution with good yields.

The nitrido-chloro complexes X[MNCl 4 ] (M = Mo, W; X = NMe 4 , AsPh 4 ) were prepared by the reaction of NMe 4 Cl and AsPh 4 Cl with MoNCl 3 and WNCl 3 , respectively. The complexes were characterised by their IR spectra; they contain M=N-triple bonds.

Rhenium(VI) nitridochloride, ReNCl 3 , is prepared by the reaction of ReCl 5 with chlorine azide. It forms a black powder with a rhenium-nitrogen triplebond (vReN 1080 cm -1 ) and a magnetic moment of 1,75 B.M.

The new ternary selenide Mg 5 Al 2 Se 8 has been prepared and structurally characterized. It crystallizes orthorhombic with α = 1330 ± 3 pm, b = 632 ± 2 pm and c = 772 ± 2 pm, space group Pna2 1 –C . The relations to the Mg 2 SiO 4 and Li 3 PO 4 structure are demonstrated.

1,2 - Diphenyl - 3,3 - dimethyl - diphosphirane (1,2- Diphenyl- 3,3- dimethyl-diphosphacyclopropane) (1) is formed by the reaction of K(C 6 H 5 )P–P(C 6 H 5 )K with 2,2-dichloropropane in n-pentane at —30 °C. It could be detected and identified by its 31 P NMR singlet at —122 ppm, which lies in the high field region characteristic for phosphorus three-membered ring compounds, as well as by its mass spectrum. Besides, (PC 6 H 5 ) 5 and several cyclocarbaphosphanes of ring sizes five and six are formed. After the reaction of (CH 3 ) 3 Si(C 6 H 5 )P–P(C 6 H 5 )Si(CH 3 ) 3 with methylene iodide a weak 31 P NMR signal at —147 ppm could be observed, which probably corresponds to the 1,2-diphenyl-diphosphirane.

The hydrolysis equilibria of Nd 3+ ion in light- and heavy-water solutions containing 3 mol dm -3 (Li)ClO 4 as an ionic medium were studied at 25 °C by measuring the lyoniumion concentration with a glass electrode. Analysis of the emf data indicated the formation of only the mononuclear complex Nd(OL) 2 + in both light and heavy water. The formation constant *β 2,1 was smaller in D 2 O (log *β 2,1 = —16.54 ± 0.04) than in H 2 O (log *β 2,1 = —15.90 ± 0.06). The formation constant K 2,1 for the heavy-water system (log K 2,1 = 12.28) had a larger value than that for the light-water system (log K 2,1 = 11.86).