Band 35, Heft 10

Without being able to stop the reaction on the first or second stage, trisamino substituted cyclotri(λ 3 -phosphazanes) (2) can be shown to add always three mole equivalents of sulfur under very mild reaction conditions to give cyclotri(λ 5 -phosphazanes) (3). Suggesting the reaction to be stereospecific, 3 shows the same 31 P NMR pattern as the starting materials 2. From this result and from molecular models, 3a-c as well as 2a-c are assumed to have diequatorial axial-substitution, whereas the bicyclic 2d and 3d are likely to have their phosphorus substituents in a diaxial-equatorial position.

(-)-Menthol, Diastereomeric Menthylesters of Phosphinic Acids, 31 P NMR Spectra, 13 C NMR Spectra, Double Resonance (-)-Menthol and diastereomeric (-)-menthyl esters of t-butyl-phenyl-phosphinic acid are investigated by means of 1 H, 13 C and 31 P NMR at 2.1 and 8.4. Tesla double resonance experiments are described.

The structure of the title compound has been determined from X-ray diffractometer data. It is isostructural with the cobalt derivative [1].

2,6,15,19-Tetrathia[7,7]paracyclophane reacts with salts of the soft acids Hg 2+ , Ag + , Pt 2+ and Pd 2+ to give polymeric complexes which are insoluble in all common solvents. As expected, no products are obtained with hard acids like Li + , Na + , K + , Rb + and Cs + .

The photochemical reaction of carboxylic acid azides and azido carboxylic acid esters, respectively, with η 5 -C 5 H 5 Mo(CO) 3 CH 3 in CH 2 Cl 2 seems to be a general route to the nitrene bridged complexes η 5 -C 5 H 5 (O =)Mo-μ(O)-μ(NCOR)Mo(= O)-η 5 -C 5 H 5 and η 5 -C 5 H 5 (O =)Mo-μ(O)-μ(NCOOR)Mo (= O) - η 5 -C 5 H 5.

Variable temperature EPR spectra of KNiIO 6 · 0.5 H 2 O have established that the paramagnetic behavior of this compound (~ 1 BM) is due to the presence of nickel(III) atoms which have occupied some nickel(IV) sites in the crystal lattices. Change of spectral pattern from rhombic (77 K) to isotropic (300 K) is due to a dynamic Jahn-Teller effect. Electrical conductivity measurement has shown it to be a poor semiconductor. KNiIO 6 · 0.5 H 2 O on heating at 300 °C forms K 2 Ni 2 I 2 O 9 which is stable in the temperature range 300-400 °C. Chemical reactivities and reflectance spectrum of this compound have indicated it to be K 2 Ni 2 II I 2 VI O 9 .

The crystal and molecular structure of dodecamethyl bisimidotriphosphoramide mono-hydrate (TRIPA • H2O, C12H38N7O4P3) has been determined by single crystal X-ray diffraction techniques. The compound crystallises in the monoclinic system, space group P2i/n with a = 9.236(3), b = 14.016(4), c = 17.534(5) A, β = 97.32(4)°, Z = 4. The building units are dimers of TRIPA • H2O. These units are separated by normal van der Waals distances. The two molecules in the dimer are connected by four hydrogen bridges involving two water molecules. The nitrogen atoms display a nearly planar hybridisation.

The interaction of the transition metal dimethylarsine sulfides Cp(CO) 2 PMe 3 M-As(S)Me 2 (M = Mo, W) with acetylhalides yields cationic complexes bearing the Me 2 AsSC(O)Me or Me 2 AsCl(Br) ligand, respectively. In a first step, the salt [Cp(CO) 2 PMe 3 M-AsMe 2 SC(O)Me] ⊕ X ⊖ 1a-c (X = Cl, Br) is formed, which is converted by a second mole MeC(O)X into salts [Cp(CO) 2 PMe 3 M-AsMe 2 X] ⊕ X ⊖ 2a-c, with (Me 2 CO) 2 S elimination. The brominated complex 2b can also be obtained by the addition of Br 2 to Cp(CO) 2 PMe 3 W-AsMe 2 . The composition and structure of the ionic dihalogen adducts are established by NMR and IR data and by conductivity measurements.

The NMR data of this new class of compounds indicate in comparison to 1,3,2-dithia-borolanes, that the heterocycle can be looked at as a 6 π-electron system. A high degree of analogy in the mass spectrometric fragmentation of dithiaborolanes and dithiaborols exists, however, the parent ion of 2-methyl dithiaborol is more stable than that of the saturated analogon.

1,2,4,3 λ 3 -Triazaphospholes unsubstituted at the heteroatoms can be synthesized only if they carry an amino group in 5-position. The title compound, being the first representative, was prepared from N,N-dimethyl-N′-aminoguanidinium iodide and P(NMe 2 ) 3 . Its single proton is not bonded to phosphorus but to nitrogen and causes association by NH···N bridges. The proton was substituted for silyl, stannyl, phosphino and thiophosphinyl groups assumedly in 2-position. The phosphino derivatives react with sulfur only at the exocyclic phosphorus. Loss of N 2 from the triazaphosphole ring was observed in one case.

The intermediacy of 3-methyl-1-boracyclopentane in the hydroboration of 3-methyl-1,3-butadiene with borane in tetrahydrofurane (BH 3 -THF) and dimethyl sulfide (BH 3 -DMS) has been established by means of 11 B NMR spectroscopy. The reaction proceeds through the trialkylborane stage (3:2 products) and the latter undergo exchange reactions with boron hydrogen compounds present. This has been proved independently by studying the 11 B NMR spectra of the mixtures between the 3:2 products and BH 3 -THF and BH 3 -DMS, respectively. Evidence is provided that opening of the boracyclopentane ring in exchange reactions is accompanied by exocyclic exchange. These results are further confirmed by the 11 B NMR spectra of the mixtures between 1-phenyl-3-methyl-1-boracyclopentane and BH 3 -THF and BH 3 -DMS, respectively. 11 B NMR spectra of the 3:2 products dissolved in DMS allow evaluation of the isomer distribution.

The existence of various intermediates in the hydroboration of 1,5-cyclooctadiene with borane in tetrahydrofurane (BH 3 -THF) is revealed by 11 B NMR spectroscopy. The presence of the THF adduct of 9-borabicyclo[3,3,1]nonane in solutions of the dimer in THF is proved for the first time, and the importance of the adduct in accelerating exchange reactions shown by 11 B NMR spectroscopy.

The preparation of new etherate and aniline compounds of the mixed complex halo-acids HCdCl 2 I and H 2 CdI 2 Cl 2 is reported. Analytical, conductometric, spectral (UV and IR) and data from X-ray powder spectra were used for the characterization of the complexes. The structure of the aniline complexes, in the solid state, cannot be deduced with certainty.

A study has been made of the Far-IR spectra (250-30 cm -1 ) of the complexes HHgI 3 · 2 Py and HHgI 3 · 2 An (Py = pyridine and An = aniline), in the solid state. Associated anionic structures are present in the two complexes. The UV spectrum of the aniline complex, in three solvents, shows that the HgI 3 - ion is the predominant anionic species in solution.

A new modification of CuI · py was prepared by the reaction of a saturated solution of CuI in CH 3 CN with a solution of pyridine in ethanol at 60 °C. It crystallizes monoclinic with four formula units in the space group P2 1 /c. (CuI · py)∞ forms a polymeric ribbon structure. Contrary to the cubane-like tetrameric modification, (CuI · py)∞ does not show luminescence thermochromism. The luminescence properties of both modifications of Cul · py are interpreted.

Bis(η 5 -cyclopentadienyl)N,N-disubstituted dithiocarbamato(chloro)oxomolybdenum(VI) complexes of the type (C 5 H 5 ) 2 MoO(S 2 CNR 2 )Cl and (C 5 H 5 ) 2 MoO(S 2 CNRR′)Cl where R = Me, Et, i-Pr and R′ = cyclohexyl (cyhx) have been prepared by the reaction of stoichio­metric amounts of bis(η 5 -cyclopentadienyl)oxomolybderium(VI) dichloride with sodium dithiocarbamates in refluxing dichloromethane. Infrared spectral studies demonstrate that in these complexes, the dithiocarbamate ligands are bidentate. Hence a coordination number of 7 may be assigned to the molybdenum(VI) atom in each case. In addition to infrared studies, electronic spectra, NMR studies, magnetic susceptibility, elemental an­alyses and conductance measurements have been carried out for these complexes.

The spinel system Zn[Fe x V 2-x ]O 4 has been prepared by heating mixtures of ZnV 2 O 4 and ZnFe 2 O 4 at 1000 °C. The lattice constants increase linearly with x by 3.6 pm, the oxygen parameters are constant with a mean value u = 0.384s. The parameters of room temperature Mössbauer spectra show that in the whole series V(III) and Fe(III) are present.

The spinel series Fe 2 VO 4 -ZnV 2 O 4 and Fe 2 VO 4 -ZnFe 2 O 4 have been prepared and investigated. The lattice constants and Mössbauer spectra lead to a distribution of cations which proves that Fe 2 VO 4 is a partially inverse spinel with Fe(II) and Fe(III) on the tetrahedral site. The Seebeck effect is interpreted with a model of both tetrahedral and octahedral conduction based on charge hopping.

The phase relations of the ternary system Ag-As-S were established by DTA and X-ray investigations. The quasibinary sections Ag 2 S-Ag 7 AsS 6 and Ag 7 AsS 6 -Ag 3 AsS 3 are described. The system Ag-As-S contains several stable compounds, including Ag 7 AsS 6 as a member of the Argyrodit family. The compounds Ag 7 PS 6 , Ag7AsS 6 , Ag7PSe 6 , Ag7AsSe 6 und AgvSbS 6 were investigated by DSC and high-temperature X-ray methods. All compounds have a phase transformation from space group P2 1 3 to F4̅3m at higher temperatures. Lattice constants and transformation temperatures are given.

The partially oxidized cis-Pt(NH 3 ) 2 (SCN) 2 I has been studied by resonance Raman spectroscopy. A progression in the symmetric I-Pt IV -I vibration (v 1 = 120.1 cm -1 ), reaching as far as 8 v 1 , has been observed. The compound Pt(NH 3 ) 2 (SCN) 2 I could be identified as a mixed valence solid with neutral, linear Pt II ···I-Pt IV chains.

[Pt(dapn) 2 ]Br 3 (dapn = 1,2-diaminopropane), ortho-rhombic, Immm (D 25 2h ), a = 5.338(1), b = 6.900(5), c= 19.738(4) Å, Z = 2, V= 727 Å 3 , d c = 2.7 g · cm -3 . The structure was refined to R = 0.094 for 576 reflections and can be described as a Wolffram's salt analogue. A rotating crystal photograph shows weak diffuse layers between the Bragg reflections as evidence for one-dimensional order along the M-X-M chain, but for successful refinement the M-X distance (2.673(1) Å) have to be assumed to be equal.

A nitromethane solution of NS + PF 6 - , obtained in situ from N 3 S 3 Cl 3 and AgPF 6 (1:3), reacts with benzene tricarbonyl chromium in acetonitrile solution to give the thionitrosyl-containing salt [Cr(NS)(NC-Me) 5 ](PF 6 ) 2 (1)-In the presence of Zerf-butyl isocyanide and Zn powder, 1 is reduced to [Cr(NS)(CN-CMe 3 ) 5 F 6 (3), while subsequent oxidation of 3 with either NOPF 6 or AgPF 6 leads to [Cr(NS)(CN-CMe 3 ) 5 ](PF 6 ) 2 (5). The thionitrosyl-containing salts 1, 3 and 5 are compared with the corresponding nitrosyl complexes.

The reactions of cyclopentadienyl dicarbonyl tetrahydrofuran manganese, CpMn(CO) 2 (OC 4 H 8 ), with either COS or COSe lead preferentially to binuclear complexes, Cp 2 Mn 2 (CO) 4 S 2 and Cp 2 Mn 2 (CO) 4 Se 2 , respectively. According to an X-ray crystallographic study, the sulfur complex is a centrosymmetric molecule containing a planar Mn-(S-S*)-Mn* unit with d(Mn-S) 216.7(4) pm, d(S-S*) 200.7(6) pm and < MnSS* 114.4(2)°.

Contrary to the reports on the coordination oi copper (I) to N/P-ambidentate cyclotri-phosphazenes, gold (I), gold (III) and dimethylgoldf 111) chloride are found to become exclusively P-coordinated to the prototype ligand 2-methyl-4,4,6,6-tetraphenylcyclotri-phosphazene (1). The P-H proton is transferred to an adjacent nitrogen atom of the heterocycle. According to temperature dependent NMR spectra, the AuCl and the AuCl 3 complexes are fluxional molecules or ions, resp., with a rapid proton transfer between P-NH-P and P = N-P functions. The behaviour is similar to that of related palladium and platinum complexes, reported previously.

The interaction of (η 5 -C 5 H 5 ) 2 MCl 2 (M = Zr, Hf) with excess C̅H 2 -P⁺Ph 3 in THF gives (η 5 -C 5 H 5 ) 2 MCl(C̅H-P⁺Ph 3 ) as yellow orange needles. Nuclear magnetic resonance spectra show hindered rotation about the P⁺-C̅ bond with ⊿G ≠ = 8.6 kcal/mole for M = Zr and 8.3 kcal/mole for M - Hf, respectively. The X-ray molecular structure of the zirconium complex shows a relatively short Zr-C bond length of 2.152 Å and a long P⁺-C̅ bond length of 1.716 Å.

Extended photolysis of M(CO) 6 (M = W, Mo) and methyl acrylate or dimethyl fumarate results in formation of (η 2 -olefin) 2 M(CO) 4 via the less stable (η 2 -olefin)M(CO) 5 complexes. X-ray structure analysis of (η 2 -methyl acrylate) 2 W(CO) 4 reveals the trans-staggered arrangement of the olefinic ligands. Rotational barriers are determined by variable temperature NMR spectroscopy.

Treatment of diethyl 1,4-cyclohexanedione-2,5-dicarboxylate (1) with hydrazine hydrate in glacial acetic acid afforded the diazobicycloocatdienedicarboxylate (2) and the azine (3). On the other hand, condensation of 1 with benzenesulphonylhydrazide in ethanolic solution gave the indazole derivative (4). Interaction of 1 with urea or hydroxyl-amine afforded the tetrahydropyrimidoquinazolinone (5) and the tetrahydrobenzodi-isoxazolone (6), respectively. Treatment of 1 with aniline gave the mono-anil (7) which, when subjected to Japp-Klingemann reaction with p-anisidine gave the dihydrazonoanil (8) and their condensation with benzidine in acetic acid gave the hydrazonoketoester (9). On the other hand condensation of 7 with hydrazine hydrate in ethanolic solution afforded the azobis (5-anilinoterephthalate) (10) and the hexahydrobenzodipyrazolone (11).

4-Arylidene-3-methyl-1-phenyl-2-pyrazolin-5-ones (1a-d) undergoes condensation with diethylmalonate, p-nitroacetophenone and/or 3-acetyl-pyridine under Michael condition to give compounds 2, 3 and 4, respectively. Treatment of 3 and 4 with hydrazine afforded the pyrazolodiazepines 7 and 8, respectively. Interaction of la with diethyl phenyl-malonate gave the Michael product 9, which undergoes hydrolysis, decarboxylation and cyclisation to give the indanone derivative (11). Condensation of 1c with hydrazine, hydroxylamine and urea gives compounds 12, 13 and 14, respectively. Cyclisation of the Michael compound 15 gives the benzopyranopyrazole (14). When 1c was subjected to Riemer-Tiemann reaction gives compounds 17 and 18. Acetic anhydride treatment of 18 gives the acetyl cresotic acid derivative (19).

Thirteen new compounds were synthesized. They are supposed to crystallize with the CaAl 2 Si 2 type of structure (space group P3̅m1) with the following constants: SrZn 2 P 2 a = 410.0(0) pm, c = 710.1(1) pm, SrCd 2 P 2 a = 433.8(0) pm, c = 726.9(1) pm, BaCd 2 P 2 a = 440.2(0) pm, c = 755.7(1) pm, BaCd 2 As 2 a = 451.6(0) pm, c = 769.3(1) pm, BaMg 2 P 2 a = 436.7(1) pm, c = 758.0(3) pm, EuZn 2 P 2 a = 408.7(1) pm, c = 701.0(1) pm, EuZn 2 As 2 a = 421.1(1) pm, c = 718.1(1) pm, EuZn 2 Sb 2 a = 448.9(1) pm, c = 760.9(1) pm, YbZn 2 As 2 a = 416.0(1) pm, c = 696.1(1) pm, YbZn 2 Sb 2 a = 444.4(1) pm, c = 742.4(1) pm, LuZnCuAs 2 a = 407.1(1) pm, c = 663.4(1) pm, YZnCuP 2 a = 398.3(1) pm, c = 652.3(1) pm, YZnCuAs 2 a = 410.4(1) pm, c = 669.2(1)pm.

The copper complex [Cu(en) 2 (Cu I 4/2 ) 2 ] crystallizes monoclinically in the space group C2/m with a = 1039.4(4) pm, b = 1337.5(3) pm, c = 656.7(2) pm, β = 117.51(2)° and Z = 2 formula units. The crystal structure is built up by cations [Cu(II)(en) 2 ] 2+ and anionic chains of edge-sharing tetrahedra [Cu(I) I 1/2 - ] n which are weakly connected by a short distance d(Cu(II) ··· I) = 340.2 pm.

Three ternary compounds PrLi 2 P 2 , PrLi 2 As 2 and NdLi 2 As 2 have been prepared and investigated by X-ray methods. They are isotypic and crystallize trigonally in the CaAl 2 Si 2 -structure (Space group P3̅m1-D 3d 3 ) with the follow-ing cell parameters: PrLi 2 P 2 : a = 419.6 pm, c = 682.1 pm; PrLi 2 As 2 : a = 429.9 pm, c = 696.0 pm; NdLi 2 As 2 : a = 428.7 pm, c = 692.2 pm.

From [Re(CO) 5 SO 2 ] + AsF 6 - or Re(CO) 5 FAsF 5 and oxygen-σ-donors D (D = H 2 O, CH 3 OH, (CH 3 ) 2 CO) the complexes [Re(CO) 5 D] + AsF 6 - are formed in quantitative yield. The spectroscopic properties of the cations are reported.

The two stereoisomeric α-azidochalkones (1,3-diaryl-2-azidopropenones) are selectively obtain-able, depending on the temperature, by condensation of aldehydes with a-azidocarbonyl compounds. For the higher melting point compound the trans configuration is proved by single crystal X-ray analysis of its triphenyl-phosphazeno derivative. Analogous isomers may now be characterised from their 1 H NMR parameters.

Dibenzo[b,def]chrysene-7,14-dione (1) and benzo[rst]pentaphene-5,8-dione (2) on vacuum flow pyrolysis successively eliminate two CO's forming 13H-naphtho[3,2,1-cd]fluoranthene-13-one (3) and finally indeno[1,2,3-cd]fluoranthene (dibenzopyracylene) (4).