Volume 28, Issue 5-6

The IR and Raman spectra of the anionic fulminate complexes [M (CNO) 4 ] 2 - (M =. Ni, Pd, Pt; Zn, Cd, Hg), including also by 11 N substituted fulminate ligands, are reported. The results are consistent with high symmetry of these anions (D 4h : M=Ni Pd, Pt; Td: M=Zn, Cd, Hg), i. e. with linear metal-C≡N- O groups.

A crystalline silicic acid H 2 Si 14 O 29 · 5H 2 O has been prepared by topochemical reaction of sodium silicate Na 2 Si 14 O 29 ·12H 2 O with acids. The compound has a layer structure with silicate sheets of about 11.2 Å thickness. The layer structure is clearly established by two dimensional reactions, mainly the formation of intercalation compounds with X-oxides (dimethylsulfoxide, pyridine-N-oxides etc.), acid amides, urea and its derivatives and bases such as hydrazine and pyridine. Typical exemples are 2 (CH 3 ) 2 SO · H 2 Si 14 O 29 , 2C 5 H 5 NO · H 2 Si 14 O 29 , 2, 7 HCONHCH 3 · H 2 Si 14 O 2 9; 2, 3 HCON (CH 3 ) 2 · H 2 Si 14 O 29 ; 1, 6 HCONHC 2 H 5 · H 2 Si 14 O 2 9; 1, 6 HCON (C 2 H 5 ) 2 · H 2 Si 14 O 29 .

Synthesis and properties of an uranylvanadate (M z+ 1/z (H 2 O) π [UO 2 V 3 O 9 ]-) with trimetavanadate ions are described. The compound has a layer structure with [UO 2 V 3 O 9 ] - -layers of about 6.5 Å thickness. The layers are identical with the U, V-layers in natural uvanite. The cations M z+ between the [UO 2 V 3 O 9 ] - -layers can be exchanged against inorganic and organic cations. The water molecules can be replaced by other solvent molecules (nitromethane, acetonitrile, dimethylsulfoxide, N-methylformamide, ethylene glycol etc.) under formation of distinct layer solvates. Reversible dehydration of the hydrates between 100° and 500°C leads to regular displacements of the uvanite layers to each other.

LiSn crystallizes monoclinic: a = 5.17 ± 0.02 Å; b = 7.74 ± 0.02 Å; c = 3.18 ± 0.02 Å; γ = 104.5° ± 0.3°, space group: P 2/m - C 2h 1 . LiSn is not isotypic with LiGe and LiPb, but there are many structural relations to LiPb.

Intercalation compounds with the limiting composition (n - C n H 2n+1 NH 2 ) x · TiS 2 with x = 0.95 - 1.02 for n = 4 - 10 and x = 1.05 for n ≥ 16 are formed from crystalline titaniumdisulfide and liquid n-alkylamine. The guest molecules are arranged in bimolecular layers between the layers of the host lattice; the tilting angle of n-alkylchains from 4 to 9 carbon atoms per chain is 56°; with 16 or more carbon atoms in the chain they stand perpendicular to the layers of the host lattice. With intermediate chain lengths random sequencies of both structures have been observed. Preparation of the compounds is facilitated by a two-step reaction:

Layer-silicates of the kaolinite type (kaolinite, nacrite, dickite, halloysite) can incorporate pyridine-N-oxide and picolin-N-oxides inbetween the silicate layers, thus forming intercalation compounds. The paper deals with the preparation of the compounds, their compositions, the increase of the basal spacings and the arrangement of the guest molecules within the host-lattice.

The ionization energies of some iron-sulphur compounds are reported and discussed. The nature of the chemical bond between iron and sulphur varies between ionic and practically pure covalent. Multiplet-splittings in the Fe3s level are observed in the photoionization resulting from the spin orientation of the 3d electrons. Satellite lines, which can be explained in terms of a shake-off process, were observed for the first time in the Fe2p and Fe3p levels of KFeS 2 . Some of the investigated compounds show satellite lines in the Fe2p level; these can be accounted for in terms of valence electron excitations.

The hitherto unknown compound BaAg 6 O 4 was prepared by high pressure reactions. A single crystal X-ray examination made obvious that the BaAg 6 O 4 compound is isotypic with the compound SrAg 6 O 4 . A detailed discussion of the relations between the structures of BaAg 6 O 4 , Ag 2 O, BaCu 2 O 2 and BaO is given.

Cl 2 VO (O 2 PCl 2 ) · POCl 3 (1) can be prepared either by the reaction of VOCl 3 with P 2 O 3 Cl 4 or by the treatment of a solution of VOCl 3 in POCl 3 with Cl 2 O Cl 2 V (O 2 PCl 2 ) 2 (2) is obtained from VCl 4 and P 2 O 3 Cl 4 . While the PO 2 Cl 2 group functions as a chelate in (1) leading to a monomeric complex, this same group forms bridges in (2) enabling polymerisation to take place.

The formation of the polyoctamolybdate ion [Mo 8 O 6- ]n results from two condensation principles. First the octamolybdate ion [H 2 Mo 8 O 28 ] 27 6- is formed by stepwise aggregation according to the condensation mechanism formerly proposed 2 . This species is subjected to a polycondensation resulting in an octamolybdate chain. The structure of the octamer unit predicted from the condensation mechanism has recently been confirmed by experiments 10 .

The IR spectrum of Na 2 [Cr(CO) 5 ], which has been obtained by reaction between Cr(CO) 6 and sodium in liquid NH 3 , is discussed. The oxidation to Na 2 [Cr 2 (CO)10] in THF has been followed IR spectroscopically. The reactions between Na 2 [Cr(CO) 5 ] and Mo(CO) 6 , W(CO) 6 and Fe 2 (CO) 9 lead to the mixed binuclear carbonylmetallates Na 2 [(OC) 5 Cr - Mo(CO) 5 ], Na 2 [(OC) 5 Cr -W(CO) 5 ] and Na 2 [(OC) 5 Cr - Fe(CO) 4 ].

The actual aspect of knowledge on the state of copper ammine complexes in aqueous solution was discussed. It was concluded, that the Cu(II)-ion has the coordination number of 5 contrary to the value of 6 assumed today. The structure of CuN 5 -chromophores in aqueous solution indicate, that the development of the penta-ammine effect is based on their higher ligand fields symmetries forced by formation of CuN 5 -chromophores comparised with CuN 4 -chromophores.

The nitrosolates of acetic and benzoic acids can be stabilized by bulky cations such as NR 4 + (R = CH 3 , C 2 H 5 ) and E (C 6 H 5 ) 4 + (E = P, As). These compounds are ionic, while those with SbR 4 + (R = CH 3 , C 6 H 5 ) are either ionic or covalent, depending on the solvent. The synthesis of all compounds mentioned is described.

ESR has been used in the study of iron(I)-nitrosyl complexes with organic ligands in solution. Four types of complexes have been identified on basis of the ESR parameters, namely Fe (NO) L 5 , Fe (NO) L 2 , Fe (NO) 2 L 2 , and Fe (NO) 2 L. In the iron-nitrosyl complexes with the organic ligands used, the groups more often involved in the coordination are: - C -NH 2 ; - C -NH; -C= O; and - C = S (eventually in the tautomeric forms). Urea and derivatives, either in water or in ethanol solutions, seem to give rise only to Fe (NO) 2 L 2 type complexes. Similar results were obtained with phenylamino-derivatives and heterocycles. Equilibria between different types of complexes - Fe (NO) L 2 and Fe (NO) 2 L - were established with hydrazides and substituted hydrazides.

Irradiation of cis-M. (CO) 4 L′ 2 (M = Cr, Mo, W; L′ = 1,3-dimethyl-4-imidazoline-2-ylidene) in solution leads to photoisomerisation to the corresponding trans-M (CO) 4 L′ 2 complexes which are reconverted thermally to the thermodynamically more stable cis-isomers. In the presence of pyridine, the photoreaction of cis-Mo (CO) 4 L′ 2 results in the formation of both fac-Mo (CO) 3 (py) L′ 2 and trans-Mo (CO) 4 L′2.

1,2,4,5-Tetrabromo-benzene and NaP(C 6 H 5 ) 2 (molar ratio 1 : 4) reacts in liquid ammonia under deposition of 4 moles NaBr. But instead of the expected compound 1,2,4,5-tetrakis (diphenylphosph ino) benzene, bis (diphenylphosphino)amine was formed. [(C 6 H 5 ) 2 P] 2 NH was characterized by mass-, IR- and 1 H-NMR-spectra and also by the reaction with chromiumhexacarbonyl.

GeJ 2 and SnJ 2 react with [C 5 H 5 Co (NO)] 2 to give C 5 H 5 Co (NO) Ge J 3 and C 5 H 5 Co (NO) Sn J 3 respectively. The same compounds are obtained in higher yields by inserting GeJ 2 and SnJ 2 into the Co- J bond of C 5 H 5 Co (NO) J. In contrast to C 5 H 5 Co (NO) Hal the new complexes C 5 H 5 Co (NO) E J 3 do not associate via NO-bridges.

The ligands T.P.A.I.* and T.B.A.I.** have been synthesised and their dissociation constants are 1.738 · 10 -10 and 1.412 · 10 -8 respectively. The potentiometric studies show that these reagents form 1 : 1 complex with copper(II) and iron(II). The stability constants of copper complex and iron complex with T.P.A.I. are 6.43 and 6.51 respectively and for T.B.A.I. 4.36 and 4.24 respectively. The free energy of complex formation at 25°C are 8.76 Kcal/mole and 8.87 Kcal/mole for Cu (II)-T.P.A.I. and Fe (II)-T.P.A.I. respectively, whereas the free energy of the Cu (II)-T.B.A.I. and Fe(II)-T.B.A.I. are 5.94 Kcal/mole and 5.78 Kcal/mole respectively.

Monohydrazones of N-(2-acetyl-1,3-indandione) quaternary iodides have been synthesised and used as reagents for carbonyl group. Aldehydes, ketones, keto-acids and cyclic ketones react with these compounds producing a yellow colour. Carbonyl compounds can be identified by the absorption spectrum of their derivatives with these reagents. The IR studies of these reagents have also been carried out.

The serine phosphoric acid P-methylester (SPM) and the ethanol-amine phosphoric acid P-methylester (EPM) were synthesized as water soluble models for the functional groups of the corresponding phospholipids. Investigations were made of the aqueous solutions of these molecules as a function of deprotonation and protonation. An intramolecular, easily polarisable hydrogen bond occurs in the zwitterion of the SPM. The solutions of different salts of SPM were studied as well as the influence of counter ion pairs. Counterion pairs hardly influence these bonds. At about 50% deprotonation extremely easily polarisable intermolecular bonds form. At about 100% deprotonation of the zwitterion the hydrogen bonds observed are affected by the presence of CO 2 . The above is indicated by changes of the bands of the carboxylic and phosphate groups, and in particular by a continuous absorption in the infrared spectrum. During protonation of the EPM easily polarisable intermolecular POH + ... OP hydrogen bonds form at first, but as protonation increases the solutions become acidic, that is, H 5 O 2 + groupings form.

Many investigations have been carried out on the electrical properties of p-terphenyl 1-9 , and, as far as we know, only one on m-terphenyl 10 . In the present work, the d. c. electrical conductivities of the three isomeric terphenyls are compared to establish the influence of the molecular structure on the electrical properties and to explain the mechanism of the energy transport in organic molecules.

Pyridinium salts of strong acids are usefull reagents in organic solvents, e. g. methanol, for the selective cleavage of acid labile amino-protecting groups as the trityl, o-nitrophenylsulfenyl, and the 2-(ρ-biphenyl)-isopropyloxycarbonyl residue. The cleavage reactions are investigated with respect to time, temperature, concentration of the reagent, different solvents, different pyridinium salts with and without addition of indole, and sterically hindrance by the structure of the amino acids.

The photolysis of N-aryl-carbamic acid alkyl esters in methanol was investigated. The primary products, amino-benzoic acid esters and aromatic amines, result from photo-Fries rearrangements and splitting processes. 2,4,6-Trimethylphenyl-carbamic acid ethyl ester and N-alkyl-carbamic acid alkyl esters form photolysis products only through homolytic splitting reactions. The photooxidation of N-substituted urethanes has been investigated in tert.-butanol. The main products are primary amines and CO 2 . These initially formed compounds are then further oxidized. In the aliphatic substituted derivatives, oxidation of the N-alkyl group results followed homolytic bond splitting.