Volume 49, Issue 2

The reactions of 1,3,5-trimethylbiuret with dicyclohexylaminodichlorophosphine and with pyrrolidinodichlorophosphine furnished the triazaphosphinane-diones 1 and 2. Oxidation reactions of the 2-diorganoam ino-1,3,5-triorgano-1,3,5-triaza-2 λ 3 -phosphinane-4,6-diones 1, 2, and 4-9, as well as 2-fluoro-1,3,5-trimethyl-1,3,5-triaza-2λ 3 -phosphinane-4,6-dione 10 with hydrogen peroxide, elemental sulphur, phenyl azide, 1-adamantyl azide,p-nitrobenzoyl azide, tetrachloro-orthobenzoquinone, tetrabromo-orthobenzoquinone, 3,5-di-t-butyl-orthobenzoquinone, and hexafluoroacetone led to the respective oxidation products, 12-32, involving either λ 4 P or λ 5 P. In the reaction o f the P(III)C1 derivative 11 with 3-m ethyl-l,5-diphenyl-l,5- bis(trimethylsilyl)biuret the bifunctional compound 33 was produced. The new com pounds 1,2 and 12-33 were characterized via their 1 H, 13 C and 31 P and, where appropriate, 19 F NMR spectra. In the case o f the four compounds, 3 (previously described in the literature [2]), 13, 31, and 33, single crystal X-ray diffraction studies were conducted. Unusually for this type of heterocycle 3 displays a 1,4-diplanar ring conformation because o f the bulky aromatic substituents. 13 shows an envelope conformation. The hydrogen peroxide solvent molecule has crystallographic inversion symmetry, but may be disordered. In 31 the coordination geometry at phosphorus is trigonal bipyramidal. The five-membered ring shows a twist conform ation associated with the bulky trifluoromethyl groups. The exocyclic P-N bonds in 33 are unusually long.

The reactions of 1,3,5-trimethylbiuret with methyldichlorophosphite, and of 2-chloro- 1.3.5-trimethyl-1,3,5-triaza-2λ 3 -phosphorinane-4,6-dione 1 with methanol or methoxytrimethylsilane furnished the methoxy-substituted triazaphosphorinane-dione 3. In the reaction of 2-hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ 4 -phosphorinane-4,6-dione 2 with diethylaminotrimethylsilane the corresponding trimethylsiloxy-substituted triazaphosphorinane- dione 4 was formed. The reactions of 3 and 4 with sulphuryl chloride gave 2-chloro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ 4 -phosphorinane-4,6-dione 5, whose synthesis via another route was described previously [7]. In the reaction of 1 with 4 the λ 3 P-O-λ 3 P-bridged compound 6 and trimethylchlorosilane were formed. Condensation reactions of the P(:O)C1 compound 5 with 2-chloroethylamine hydrochloride and bis(2-chloroethyl)amine hydrochloride in the presence of triethylamine furnished the amide derivatives 7 and 8. Compounds 3-5, 7 and 8 were characterized via their 1 H, 13 C, 31 P NMR and mass spectra, compound 6 was characterized from its 1 H and 31 P NMR spectra only.

The reaction of 5,6-benzo-2-chloro-1,3-dimethyl-1,3,2-diazaphosphorinane-4-one (1) with trimethylsilyl azide led to the substituted cyclotriphosphazene (3). A monomeric reaction product was not observed by NMR spectroscopy. The diazaphosphorinane 2, with the 2-chloroethyl substituent bonded to the nitrogen atom in a-position to the carbonyl group, did not react with trimethylsilyl azide. An attempt to prepare 3 from N,N'-dimethylanthranilamide 5 and hexachlorocyclotriphosphazene 4 failed, as did the attempt to react 5 with phosphorus pentachloride. The reaction of 5,6-benzo-2-{bis(2-chloroethyl)amino}-1,3-dimethyl- 1.3.2-diazaphosphorinane-4-one (7) and of the related compound 9, bearing only one 2-chloroethyl substituent, with 4-nitrobenzoyl azide furnished, in a normal Staudinger fashion, the monomeric products 8 and 10. In the case of 10, intramolecular P=O···H interaction was demonstrated by IR spectroscopy.

The reaction of [VO(dipic)(H 2 O) 2 ]·2H 2 O with benzoylhydrazine, thiobenzoylhydrazine and O-methylcarbazate yields [V(dipic)(NH 2 NHCOPh)(H 2 O)2][VO(dipic)(NHNCOPh)·2H 2 O (1), [V0(dipic)(NHNHCO 2 Me)] (2), [VO(dipic)(NH 2 NHCO 2 Me)] (3) and [VO(dipic)(NHNHCSPh)] (4). 1 is probably formed in solution by redox disproportionation. The reactions giving 2,3 and 4 also involve redox processes with atmospheric oxygen as oxidant and the respective hydrazine as reductant. [VO('ONO')(NHNHCOPh)]·H 2 O (5) was formed using aqua-oxo-salicylaldehyde-L-alaninato-vanadium(IV) as precursor. The structures of 1,2,3 and 5 have been determined by single crystal X-ray crystallography. The cation of 1 has a seven-coordinated vanadium(III) center with the two H 2 O molecules at the apices of a pentagonal bipyramide, the anion contains the doubly deprotonated hydrazido( 2-) ligand NHNCOPh 2- as N,O-chelate. 2 and 3 have very similar structures, but differ in the oxidation state of the vanadium atom and in the degree of deprotonation of the hydrazine. In 3 neutral NH 2 NHCOOMe and in 2 the single deprotonated hydrazido(l -) ligand NHNHCOOMe- are bound as N,O-chelates, with the O-donor in rrans-position to the VO group. The remaining coordination sites are occupied by the ONO-donating dinegative dipic ligand. 5, where dipic is replaced by the three-dentate salicylaldehyde-benzoyl-hydrazone, has a very similar structure to 2. 4 with a VO 3 N 2 S coordination sphere is the first vanadiun (V) complex containing the N,S-donating hydrazido(l-) ligand NHNHCSPh-. The following parameters are characteristic for the bonding of the NHNHR- and NHNR 2- ligands in 1,2 and 5: V-N 189 ± 1 pm, N-N 134 ± 1 pm and V-N-N 122 ± 2°.

8-(Phenylamino)-l-naphthalene-silver sulfonate 2 was prepared from the corresponding ammonium salt 1 and silver nitrate under ambient conditions in ethanol. From 2 salts with several other monovalent cations were obtained. All of them show similar fluorescence properties. Attempts to esterify the sulfonate group by means of alkylhalides were unsuccessful. Only after prolonged reaction times several decomposion products were detected in the TLC.

The crystal structure of Na 2 Ba was determined from single crystal X-ray diffraction data. It is isostructural with the hexagonal Laves phase Zn 2 Mg; P6 3 /mmc, a = 739.3(4) pm, c = 1199.9(9) pm. The compound Na 4 Ba reported in the phase diagram literature is actually Na 2 Ba. Comparisons are made with other Laves phases using a strain parameter diagram.

Indium tris(thiocarbamates) In(S 2 CN i Pr 2 ) 3 (1), In(SOCN i Pr 2 ) 3 (2) and In(S 2 CNC 4 H 4 ) 3 (3) have been synthesized and characterized. Variable temperature 1 H NMR spectra of 1 and 2 are reported. The X-ray molecular structures of 1 and 3 are found to be quite similar; the symmetry of the In(S 2 C) 3 unit in 3 is close to point group D 3 with small asymmetry in the In-S bonds.

Bis[bis(trimethylsilyl)methyl]-as well as bis(2,2,4,4,6,6-hexa-methyl-2,4,6-trisila-cyclo-hexyl)zinc react with methyl lithium or phenyl lithium in the pres­ ence of the tridentate l,3,5-trimethyl-l,3,5-triazinane (TMTA) to yield zincates of the type LiZnR 2 R'·2TMTA. The compounds are colorless and insoluble in aliphatic or aromatic hydrocarbons. These zincates exist in solution as well as in the crystalline state as separated ions, as confirmed for lithium-methyl-bis(2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl)-zincate · 2TMTA by X-ray diffraction (P1̄; a -1139,5(3); b = 1482,4(4); c = 1528,6(5) pm; α = 95,33(2); β = 100,13(2); γ = 106,91(2)°; Z = 2). The lithium cation is six-coordinated by two TMTA ligands in a distorted anti-prismatic complex. The zinc atom displays a trigonal planar coordination with Zn-C bond lengths of 207 pm to the 2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl ligands and of 202 pm to the methyl group. One trisila-cyc/o-hexyl substi­ tuent exists in the chair, the other one in the twist conformation. The reaction of lithium bis(trimethylsilyl)amide with bis(trimethylsilylmethyl)zinc yields the benzene soluble lithium-bis(trimethylsilyl)amino-bis(trimethylsilylmethyl)zincate TMTA. The molecular structure was confirmed by X-ray diffraction (P2 1 2 1 2 1 ; a -1024,8(3); b = 1775,4(7), c = 1918,2(8) pm; Z = 4). The bridging bis(trimethylsilyl)amino ligand displays long Zn-N and Li-N distances of 213 and 208 pm, respectively, due to the steric inter-ligand repulsion. During the reaction of lithium bis(trimethylsilyl)amide with bis[bis(trimethylsilyl)methyl]-zinc no zincate formations observed. The decomposition products lithium bis(trimethylsilyl)-methanide and the heteroleptic bis(trimethylsilyl)amino-bis(trimethylsilyl)methylzinc were detected.

Colourless crystals of the 1,4,8,11-tetraazacyclotetradecane (cyclam) silver(I) thiocyanate complex [Ag(SCN) · (C 10 H 24 N 4 ) 1/2 ] were obtained by diffusion of a solution of cyclam in ethanol into an aqueous solution of K[Ag(SCN) 2 ], The crystals are tetragonal, space group P4 2 /n, Z = 8, a = b - 1256.0(4), c = 1185.5(9) pm. The SCN groups act as μ 3 ligands, the S atoms of two SCN groups bridge two neighbouring Ag ions, which are only 297.5 pm apart, forming butterfly-like Ag 2 S 2 moieties, the N atoms of the SCN groups form bonds to Ag atoms of adjacent Ag 2 S 2 moieties. Two Ag 2 S 2 units are again connected by cyclam molecules which act as two-dentate bridging ligands. Thus a complicated three-dimensional “supramolecular” structure results.

The X-ray crystal structure analysis of the silver icosadiborate hydrate, Ag 2 O · 11 B 2 O 3 · 5 C 2 H 4 (NH 2 ) 2 · 20H 2 O (triclinic, P1̄, a = 842.4(1), b = 868.5(1), c = 2160.6(2) pm; α = 79.5(1), β = 85.4(1), γ = 86.4(1)°, Z = 1), shows that the unit cell contains two anions of heptaborates [B 7 O 9 (OH) 5 ] 2- , two anions of tetraborates [B 4 O 5 (OH) 4 ] 2- , and eight molecules of crystal water as well as probably one cation of disilver(I)-tris(ethylenediamino) [(Hen) + Ag + (en) Ag + (enH) + ] and two cations of ethylenediammonium (HenH) 2+ .

PHal 3 X + MF 6 - (Hal = Cl, Br; X = H, D; M = As, Sb) are prepared at 213 K by protonation of the phosphortrihalides in the superacidic media XF/MF 5 . The salts are characterized by 31 P, MS, IR and Raman spectroscopy.

(η5-C 5 Me 5 ) (M - Co, Rh, Ir) and (η5-p-cymene)(CI) have been obtained by reactions of (η5-C 5 Me 5 )Co(CO)I 2 , [(η 5 -C 5 Me 5 )MCl 2 ] 2 (M = Rh, Ir) and [(η 6 -p-cymene)RuCl 2 ] 2 with 2-hydroxyiminocarboxylates. These complexes are also accessible by template synthesis from hydroxylamine or O-methylhydroxylamine, α-oxocarboxylate and (η 5 -C 5 Me 5 )Co(CO)I 2 or [(η 5 -C 5 Me 5 )MCl 2 ] 2 (M = Rh, Ir). The structure of the S Ru enantiomer of (η 5 -C 5 Me 5 )(I) has been determined by X-ray diffraction.

In the HgF 2 -assisted addition of Cl 2 and Br 2 to C 6 F 5 CN the compounds C 6 F 5 CF=NX (3, 5: X = Cl, Br) and C 6 F 5 CF 2 NX 2 (2, 4: X = Cl, Br) are formed. Photochemical decomposition of the dibromoamine (4) gives the diazene C 6 F 5 CF 2 - N=N - CF 2 C 6 F 5 (6) in 31% yield. The structure of 6 has been determined by X-ray diffraction.

The preparations of [Mg(NSF 3 ) 4 ](AsF 6 ) 2 (2a) and [Zn(NSF 3 ) 4 ](AsF 6 ) 2 (2b) are reported. The structure of 2b was determined by X-ray diffraction. The ligand properties of NSF 3 are discussed.

The melting diagrams of three systems alkylamine- water have been reexamined and the crystal structures of four lower hydrates determined for the first time. The hydrate EtNH 2 · 0.5 H 2 O , m.p. -72 °C, is triclinic with space group P1̄ and Z = 4 formula units per unit cell of dimensions a = 5.104, b = 8.137, c = 9.394 Å, α = 100.41, β = 98.41 and γ = 97.96° at -150°C. The O and N atoms are hydrogen-bonded into a two-dimensional array 2 ∞ [ON 6/3 ] analogous to the layer of the Cdl 2 structure type. The hydrate Et 2 NH · 0.5 H 2 O , m.p. -20 °C, is monoclinic with 12/a, Z = 8 ,a - 8.324, b = 15.090, c = 10.006 Å and β - 103.34° at -100 °C. The O and N atoms are linked into a four-membered ring spiro chain 1 ∞ [ON 4/2 ] analogous to that in SiS 2 . The hydrate l-BuNH 2 · 0.5H 2 O (m.p. -57 °C, monoclinic, P 2 1 /c, Z = 8,a = 14.994, b = 5.086, c = 16.15 Å,β - 103.45° at -81 °C) contains essentially the same hydrogen-bonded array as the hydrate EtNH 2 -0.5 H 2 O (see above). l-BuNH 2 -H 2 O , the only monohydrate investigated besides the three hemihydrates (m.p. -60 °C, monoclinic, C 2/m, Z = 4, a = 9.68, b = 4.238, c = 15.58 Å, β = 94.9° at -81 °C), has also a two-dimensional H 2 O/NH 2 partial structure, similar to a subset of the three-dimensional network of the adduct NH 3 H 2 O of analogous composition.

Trimethyltinlithium reacts with z-1,2-bis(diisopropylamino-chloro-boryl)ethene derivatives 4a (R = Et) and 4b (R = H) to give the cis-1,2-bis(diisopropylamino-trimethyltin-boryl)- hexene-3 (2a) and, surprisingly, the trans-1,2-bis(diisopropylamino-trimethyltin-boryl)- ethene (5 b) respectively. The constitution of 2 a and 5 b is derived from spectroscopic data, and confirmed by X-ray structure analyses. The formation of the trans-product 5 b probably occurs via a radial intermediate.

Reaction of the diphosphene R f P=PR f (R f = 2,4,6-tris(trifluoromethyl)phenyl-) with red selenium affords the selenadiphosphirane 1. The X-ray crystal structure of 1 was investigated.

A series o f zinc complexes of dimethyl(phthalimidomethyl)phosphine oxide (DPPO, L) have been synthesized: ZnX 2 L 2 , where X = Cl, Br, I or NO 3 . The complexes are characterized by elemental analysis, infrared and 1 H NMR spectra and X-ray powder analysis. Infrared spectral data show that L is coordinated to zinc via the phosphoryl oxygen atom. The zinc halide complexes are found to be isostructural, while the pattern o f Zn(NO 3 ) 2 L 2 differs considerably from those o f halide complexes.

Three benzil based, macrocyclic oxygen-, nitrogen-, and sulfur-containing ligands, (3,4,10,11 -tetraphenyl-1,2,5,6,8,9,12,13-octaazacyclotetradeca-7,14-dithione-2,4,9,11 -tetraene) ethanol (L 1 ), 10,1 l-diethoxy-3,4,10,11-tetraphenyl-1,2,5,6,8,9,12,13-octaazacyclotetradeca- 7.14-dithione-2,4-diene (L 2 ), (3,4,10,11 -tetraphenyl-1,2,5,6,8,9,12,13-octaazacyclotetradeca- 7.14-dione-2,4,9,l 1-tetraene) ethanol (L 3 ); a cyclic ligand, 6-ethoxy-l,6-diphenyl-4-oxo- 3,4,5,6-tetrahydro-2,3,5-triazine (L 5 ) and two open chain ligands, benzilsemicarbazone (L 6 ) and benzilbisthiosemicarbazone (L 4 ) are reported. These ligands react with copper(II) chloride, nitrate and acetate. The complexes obtained have been characterized on the basis of NMR , IR, electronic and mass spectral studies, conductance and analytical data. The stoichiometry and the spectroscopic data o f the complexes indicate that the copper ions are coordinated by neutral ligands or by ligand anions formed by loss o f protons from the ligand. The molecular and crystal structure of 6-ethoxy-l,6-diphenyl-4-oxo-3,4,5,6-tetrahydro- 2,3,5-triazine (L 5) was determined by X-ray diffraction; the space group is triclinic, P1̄ with a = 7.865(1), b = 14.101(6), c = 15.733(9) Å, α = 69.10(3)°, β = 75.62(2)°, γ = 86.69(2)°, V = 1578(1) Å 3 , Z = 4.

Diels-Alder reactions of (-)-thebaine (1) as an electron-rich diene system with acceptorsubstituted ethenes gave rise to the cycloadducts 2, 3, and 4 in high regio- and stereoselectivities. Structural analyses were performed by high resolution NMR spectroscopy and, for the first time in the thebaine cycloadduct series, by X-ray crystallographic structural analyses of the compounds 2, 3a, and 3b. In the reaction of (-)-thebaine (1) with an in situ generated aryne, the anellated azocine derivative 5 was formed.

The photodegradation of the 1,2,4-triazole fungicide Folicur 1 in different organic solvents (benzene, ether, methylene chloride, methanol) and water, in absence and in presence of a singlet oxygen sensitizer (methylene blue) has been studied. The photometabolites formed in organic solvents, have been separated by column chromatography (with isolation of 4 -7 , 13 and 14) and in the case of benzene as solvent as well with the aid of HPLC (isolated: 4 -7 , and five additional products 8-12). Photodegradation of 1 in water leads to the formation of only two photoproducts: 4 and 17 (separated only by HPLC). Identification has been achieved by spectroscopic methods and comparison (of retention times, UV and mass spectra) with authentic samples. Furthermore, the kinetics of the photodegradation of 1 in benzene and water (also after addition of titanium dioxide) has been established by HPLC-UV/VIS-technique. The interpretation of the kinetics allows conclusions towards the photodegradationmechanism, which is discussed in the paper. As expected, the addition of the photocatalyst titanium dioxide leads to a significant acceleration of the photodegradation.

1,4-Bis(trimethylsiloxy)benzene has been crystallized both by vacuum sublimation and from «-heptane solution, which each yielded colourless plates with identical monoclinic unit cell dimensions (P 2 /n, Z = 4). The conformation of C[ symmetry shows the two (H 3 C) 3 SiO-substituents to be conrotationally twisted around the O-( C 6 H 4 )-O axis by dihedral angles o f ± 60°. According to the photoelectron spectroscopic ionisation pattern and its Koopmans’ assignment, IE V n = -ε J AM 1 , by AM 1 eigenvalues, the gas phase structure should also be of C, symmetry. The results of geometry-optimized MNDO , AM 1 or PM 3 calculations for the monosubstituted derivative H 5 C 6 -OS i(CH 3 ) 3 are compared with respect to the quality of their fit to the measured data.