Band 49, Heft 7

Tris[(trimethylsilyl)oxy]antimony (Sb(OSiMe 3 ) 3 , 1) has been prepared from SbCl 3 and 3 equiv. of LiOSiMe 3 in diethylether. According to mass spectrometric and NMR spectroscopic data, 1 appears to be a monomer in solution and in the gas phase. Dimerisation occurs, however, in the solid state as verified by an X-ray crystal structure determination. The unit cell contains three crystallographically independent monomers, two of which form one type of dimer, while the other is part of a centrosymmetrical dimer. In both types of dimers two Sb atoms are connected via two OSiMe 3 groups to form distorted Sb 2 O 2 -squares. Together with the remaining 4 OSiMe 3 groups and the two stereochemically active lone pairs, each Sb exhibits a trigonal bipyramidal coordination.

Compound [RhCl(PiPr 3 ) 2 ] n (1) reacts with RC≡CSiPh 3 to give the rhodium(I) complexes trans-[RhCl(RC≡CSiPh 3 )(PiPr 3 ) 2 ] (2-5) of which 2 (R = CH 3 ) and 5 (R = C 6 H 5 ) rearrange thermally to yield the vinylidene isomers trans-[RhCl(=C=C(SiPh 3 )(R)(PiPr 3 ) 2 ] (6,7). The reaction of 2 and 4 (R = CH 2 OMe) with NaC 5 H* affords the cyclopentadienyl complexes [C 5 H 5 Rh(RC≡CSiPh 3 )(PiPr 3 )] (8,9). The square-planar alkynylrhodium(I) compounds trans-[Rh(C≡CSiPh 3 )(L)(PiPr 3 ) 2 ] (12,13) are obtained from 10 or 11 on treatment with NaN(SiMe 3 ) 2 ; they react with cyclopentadiene to give [C 5 H 5 RhH(C≡CSiPh 3 )(PiPr 3 )] (14). Five- and six-coordinate bis(alkynyl)hydridorhodium(III) complexes [RhH(C≡CSiPh 3 )(C≡CSiR 3 )(PiPr 3 ) 2 ] (15,16) and [RhH(C≡CSiPh 3 )(C≡CSiR 3 )(py)(PiPr 3 ) 2 ] (17,18) are prepared from 12 and 13 by oxidative addition of HC≡CSiR 3 (R = CH 3 , C 6 H 5 ). The reaction of 12 with Me 3 SiC≡CCO 2 Et leads to the formation of trans-[Rh(C≡CSiPh 3 )(Me 3 SiC≡CCO 2 Et)(PiPr 3 ) 2 ] (19).

The crown ether complexes SbF 3 (18-crown-6) (1), SbF 3 (18-crown-6) · CH 3 CN (2) and (SbF 3 ) 2 (12-crown-4) (3), have been prepared by reactions of SbF 3 and the corresponding crown ether. They have been characterized by IR. Raman and 121 Sb-Mößbauer spectroscopy, and by X-ray structure determinations. The s electron density at the Sb atom is diminished in these complexes. 1 and 2 show a symmetrical half-sandwich structure, with coplanar O atoms and Sb-O distances ranging from 298 to 321 pm. 3 has a band-like structure. The two metal centers adopt different stereochemistries. The Sb-O distances are in the range from 269 to 325 pm. One oxygen atom of 12-crown-4 has a bridging function. Crystal data for 1: space group P2 1 2 1 2 1 , a = 823,1(1), b = 1146,1(2), c = 1807,0(3) pm, Z = 4; 2: space group P2 1 /c, a = 1257,7(3), b = 828,9(2), c -1895,5(5) pm, β = 93,68(2). Z = 4; 3: space group P2 1 /c, a = 805,6(1), b = 2143,1(4), c = 836,4(2) pm, β = 90,98(1), Z = 4.

The cyclic organostibane oxide [(Me 3 Si) 2 CHSbO] 4 (1) has been prepared by reaction of RSbCl 2 with KOH in water/diethylether and crystallization as 1·H 2 O from petroleum ether. The crystal structure of 1·H 2 O consists of a boat shaped 8-membered Sb 4 O 4 heterocycle with the substituents in trans positions (distances Sb-O 197.0(3) pm, Sb-C 217.2(4) pm, angles O-Sb-O 93.2(1)°, Sb-O-Sb 122.3(2)°, O-Sb-C 96.2(1)°) and disordered water molecules. Crystal data: tetragonal, space group 14̅; a = 16.091(2), c = 11.057(2) Å; Z = 2.

XeF + MF 6 - (M = As, Sb) reacts with ((CF 3 ) 2 CS) 2 and Cl 2 CS to form the corresponding monofluorinated sulfonium hexafluorometalates. The salts have been characterized by vibrational and 19 F NMR spectroscopic measurements. crystallizes in the monoclinic space group C2/c with a =o 14.791(10), b = 11.093(6), c - 10.356(6)Å, β = 119.83° and Z = 4. With a value of 1.51(1) Å d (S-F) is comparable to the SF-bond distance in .

Starting from pentaglycerin, H 3 CC(CH 2 OH) 3 , a convenient three step synthesis of the tri­pod ligand H 3 CC(CH 2 PPh 2 ) 2 (CH 2 OH) (3) (abbreviated as PPO(H)) is described and its struc­ture is established by the usual analytical methods as well as by X-ray analysis. The ligand behaves as a bidentate donor towards nickel(II) as shown by the formation and X-ray analysis of the complex {PPO(H)}NiBr 2 (4). In the square planar complex 4 only the PPh 2 groups are coordinated. In the tetrahedral complex [{PPO(H)} 2 Ni](BF 4 ) 2 (5) two PPO(H) ligands sur­round nickel as bidentate ligands.

Starting from (MeO) 3 SiCH 2 Cl (10) and Ph 2 (H)SiCH 2 OH (16), respectively, the (hydroxymethyl)diphenyl(piperidinoalkyl)silanes (HOCH 2 )Ph 2 Si(CH 2 ) 2 NC 5 H 10 (6) and (HOCH 2 )Ph 2 Si(CH 2 ) 3 NC 5 H 10 (8) have been synthesized [10→Ph 2 (MeO)SiCH 2 Cl (11)→Ph 2 (CH 2 =CH)SiCH 2 Cl (12)→Ph 2 (CH 2 =CH)SiCH 2 OAc (13)→Ph 2 (CH 2 =CH)SiCH 2 OH (14)→Ph 2 (CH 2 =CH)SiCH 2 OSiMe 3 (15)→6; 16→Ph 2 (H)SiCH 2 OSiMe 3 (17)→8; NC 5 H 10 = piperidino]. N-Quaternization of 6 and 8 with MeI gave the corresponding methiodides 7 and 9, respectively. As shown by IR-spectroscopic studies, compounds 6 and 8 form intramolecular O-H···N hydrogen bonds in solution (CCl 4 ). In the crystal, 6 (space group Pna2 1 ; two crystallographically independent molecules) also forms intramolecular O-H···N hydrogen bonds whereas 8 (space group P1̅) forms intermolecular O-H···N hydrogen bonds leading to the formation of centrosymmetric dimers (single-crystal X-ray diffraction studies). The (hydroxymethyl) silanes 6-9 and the related silanols (HO)Ph 2 Si(CH 2 ) 2 NC 5 H 10 (sila-pridinol; 1), sila-pridinol methiodide (2), (HO)Ph 2 Si(CH 2 ) 3 NC 5 H 10 (sila-difenidol; 3) and sila-difenidol methiodide (4) were investigated for their antimuscarinic properties. In functional pharmacological experiments as well as in radioligand competition studies, all compounds behaved as simple competitive antagonists at muscarinic M 1 -, M 2 -, M 3 - and M 4 -receptors. In general, the silanols 1-4 displayed higher receptor affinities (up to 100-fold) than the corresponding (hydroxymethyl) silanes 6-9 . In the (hydroxymethyl)silane series, compound 7 was found to be the most potent muscarinic antagonist [pA 2 /pK i = 8,71/8,6 (M 1 ), 8,23/7,8 (M 2 ), 8,19/7,8 (M 3 ); pK i = 8,2 (M 4 )]. In the silanol series, the related compound 2 showed the most interesting antimuscarinic properties [pA 2 /pK i = 10,37/9,6 (M 1 ), 8,97/8,8 (M 2 ), 9,08/8,8 (M 3 ); pK i = 9,4 (M 4 )].

Single crystals of Ba 2 Ti3 + Cr 2 Oi 3 were prepared by C0 2 -LASER high temperature reactions and investigated by X-ray work. The compound crystallizes with monocli­nic symmetry, a = 15.0185, b = 3.9419, c = 9.0764 Å. β = 98.137°, Z = 2. Ba 2 Ti 4 Cr 2 O 13 is isotypic to Na 2 Ti 6 O 13 . The crystal structure is discussed with respect to ordered or disordered distributions of Ti 4+ and Cr 3+ using calculations of Coulomb terms of lattice energy. It is shown, that the stability of this structure type will be decre­ased by replacement of Na + by ions with higher oxidation states.

Single crystals of BaNb 3 O 6 were prepared by CO 2 -LASER high temperature technique. The compound crystallizes with trigonal symmetry C 5 3v -R3m , a = 11.4333, c = 3.4949 Å , Z = 3. The new structure type is characterized by planar NbO 4 and planar BaO 6 polygons. The results are discussed with respect to related compounds like Ca 0.75 Nb 3 O 6 or NaNb 3 O 6 .

Single crystals of (I): EuBeGd 2 O 5 , (II): Ca 0,4 Sr 0,6 BeSm 2 O 5 , (III): Ba 0,25 Ca 0,75 BeNd 2 O 5 and (IV): Ba 0.36 Sr 0.64 BeNd 2 O 5 were prepared by (I): plasma torch and (II)-(IV ): CO 2 -LASER technique. X-Rayo investigations lead to (I) monoclinic (space group C 5 2h -P2 1 /c, a = 7.126, b = 6.457, c = 9.394 Å , β = 90.40°) and (II)-(IV) orthorhombic symmetry (D 16 2h -Pnma). (II: a = 9.454, b = 7.142, c = 6.490 Å; III: a = 9.508, b = 7.188, c = 6.531 Å; IV: a = 9.642, b = 7.295, c = 6.614 Å). In contrary to the phases M 1-x M′ x BeLn 2 O 5 , EuBeGd 2 O 5 is characterized by an ordered distribution of Eu 2+ and Gd 3+ inside of the Kagomé network.

SrCo 2 V 2 O 8 (I) and SrCo 2 (As0 4 ) 2 (II) were prepared by crystallization from melts and investigated by X-ray single crystal technique. (I) is isotypic to the SrNi 2 V 2 O 8 -type and crys­tallizes with tetragonal symmetry, space group C 12 4 v-I4 1 cd, a = 12.267: c = 8.424 Å: Z = 8. (II) is isotypic to the lately found SrNi 2 (PO 4 ) 2 , space group C 1 i -P1̅, a = 5.713; b = 6.903; c = 9.417 Å: a = 110.48; β = 101.43; γ = 99.13°, Z = 2.

Single crystals of Cd 0.73 Cu 0.27 V 2 O 6 were prepared by solid state reactions. X-ray investigations lead to monoclinic symmetry, space group C 3 2h -C2/m , a = 9.339, b = 3.5604, c = 6.893 Å, β = 111.85°, Z = 2. It belongs to the Brannerite structure, showing a statistical distribution of Cd 2+ and Cu 2+ on one point position. The crystal structure of Brannerites is discussed with respect to the distorted O 2- octahedra around V 5+ and the influence of the Jahn-Teller active Cu 2+ ion to the shortened M 2+ O 6 octahedra.

Tetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 with an Al-Al bond and Et 3 P + -Te - give under mild conditions the title compound R 2 Al-Te-AlR 2 (R = CH(SiMe 3 ) 2 ) 2 in high yields. Due to the high steric shielding 2 is monomeric even in the solid state with an angled Al-Te-Al group (110.4°) and an Al-Te bond length of 254.9 pm as expected for a Al-T e single bond with the atoms in low coordination numbers. A hindered rotation of the bulky substituents is observed in solution probably caused by steric restrictions similar that in ana­logous compounds with Al-S-Al or Al-CH 2 -Al groups.

NaK 9 Tl 13 (a = 1152.0(1) pm, Im 3, Z = 1, R1 -0.029, wR2 = 0.0724) has been prepared from the elements and characterized by single crystal X-ray diffraction. The title compound contains isolated Tl 12 icosahedra, which are centered by Tl atoms. The icosahedra are in an α-W-type arrangement.

The reaction of 4,5-benzo-2-chloro-3-methyl-1,3,2-oxazaphosphorinan-6-one 1 with 1,2-bis- (trimethylsiloxy)ethane led to the bisphosphoryl species 2a and to the isomeric bisphosphite derivative 2b. The reaction of 1 with heptamethyldisilazane furnished the expected diphos­phorus compound 3, with two λ 3 P(III) atoms linked by a methylamino group. Substitution of the chlorine atom of 1 by the 2-chloroethylamino and bis(2-chloroethyl)amino group led to the oxazaphosphorinanones 4 and 6. By oxidation of 4 with the hydrogen peroxide/urea 1:1-adduct, the phosphoryl compound 5 was formed. Oxidation of 4,5-benzo-2-diethyl- amino-3-methyl-1,3,2-oxazaphosphorinan-6-one 7 [1] with hydrogen peroxide, sulfur and se­lenium led to the corresponding phosphoryl, thiophosphoryl and selenophosphoryl com­pounds 8-10. Analogously, the reaction of the dimethylamino- and acetamido-substituted derivatives 11 and 13 [1] with elemental sulfur furnished the thiophosphoryl compounds 12 and 14. X-ray crystal structure determinations of 4 and 14 confirmed the molecular structures, proposed in accord with NMR spectroscopic and mass spectrometric data. The heterocyclic rings are essentially planar. In 14 a hydrogen bond N-H···O (amide) is observed.

Metal propionate hydrazinates, M(CH 3 Ch 2 COO) 2 (N 2 H 4 ) 2 where M = Mn, Co, Ni, Zn or Cd, and mixed metal propionate hydrazinates with cobalt, M 1/3 Co 2/3 (CH 3 CH 2 COO) 2 (N 2 H 4 ) 2 where M = Mg, Mn, Ni, Zn or Cd, have been prepared and characterized by analytical, magnetic, spectral, thermal and X-ray diffraction studies. The thermal decomposition of the former complexes yields the metal oxides while the latter mixed metal complexes give the corresponding metal cobaltites as the final residue. Formation of metal cobaltites has been confirmed by TG weight loss, IR spectra and X-ray diffraction.

The complex [(n7Bu 3 P)(Cl)Pt] 3 (triquinolobenzene-3H + ) is obtained from the trisodium salt of triquinolobenzene and (nBu 3 P)(Cl)Pt(μ-Cl) 2 Pt(Cl)nBu 3 ) and has been characterized by X-ray diffraction. The three platinum atoms are syn positioned outside of the not ideal plane of the triquinolobenzene frame.

Dehalogenation of tmp 2 GaCl (tmp = 2,2,6,6-tetramethyl piperidino group) with sodium/ potassium alloy leads to the digallane (tmp) 2 Ga-Ga (tmp) 2 as a pale yellow solid. Alterna­tively this digallane is prepared in good yields by reaction of four equivalents of tmpLi with Ga 2 Cl 4 ·2 dioxane. Ga 2 (tmp) 4 is characterized by MS. NMR ( 1 H and 13 C) and X ray structure determination. The gallium-gallium bond length is 252.5(1) pm and its two GaN 2 units are twisted by 31° against each other.

Various dialdehydes (1 -5) were formed by addition of dithiols to acrolein. Reaction of these dialdehydes with N-alkylhydroxylamines afforded dinitrones the two nitrone groups of which were joined by an alkylidene chain containing two sulfur atoms (6a,b-10a,b). Cycloaddition of these dinitrones with dimethyl acetylenedicarboxylate proceeded in the usual way giving bis(4-isoxazolines) (11a-15a). However, analogous dinitrones formed by reaction of the dialdehydes with N-(4-tert-butylphenyl) hydroxylamine could not be isolated. Instead tricyclic compounds arose in which the central macrocyclic ring is flanked by two isoxazolidine rings (16c-20c). Obviously, the dinitrones formed as intermediates underwent dimerization with formation of the tricyclic compounds by cycloaddition between two nitrone groups and two tautomeric N-hydroxyenamine moieties. Two of the tricyclic compounds (16c and 20c) formed 1:1 complexes with NiCl 2 and FeCl 3 , respectively.

The sulfhydrolysis of the glycolimidates 3 affords 2-hydroxy thiocarboxylic O-esters (4), which on treatment with phenylhydrazine give glycolohydrazonates of type 5. Under suitable conditions the reaction of 5 with phosgene or 1,1′-thiocarbonyldiimidazole produces 3,6-dihydro-2H -1,3,4-oxadiazin-2-ones(thiones) 6 as stable compounds.

Venturicidin X (la ), the aglycon of the venturicidins A (1b) and B (1c) was isolated for the first time as a natural product from an unidentified Streptomyces sp. Venturicidin X (1a) is highly active against a broad spectrum of plant pathogenic fungi.

PF 3 is obtained in high purity by reacting PCl 3 with Me 3 SnF. Alternative fluorinating reagents for this reaction are Ph 3 SnF and (i-C 4 H 9 ) 3 SnF. The reaction with the isobutyl derivative is less complicated since the resulting chloride is a liquid in contrast to Ph 3 SnCl being a solid. PCl 5 , MeCOCl, SiCl 4 , Me 3 SiCl, and SOCl 2 react with Me 3 SnF to give also the corresponding fluorides. The resulting chlorides are easily converted again to the fluorides. A quantitative recycling of the fluorinating reagent is therefore achieved.

The title compound has been obtained by the reaction of the phosphoraneiminato complex Cl 2 Sb(NPPh 3 ) with chlorine, followed by partial hydrolysis in acetonitrile. The colourless crystals were characterized by a crystal structure determination. Space group P1̅, Z = 2, structure refine­ment with 8320 observed unique reflections, R = 0.063 with I > 2σ(I). Lattice dimensions at -70 °C: a = 1245.0(6); b = 1277.7(8), c = 1623.8(9) pm, a = 77.97(2)°, β = 86.52(2)°, γ = 67.07(2)°. The compound consists of Ph 3 PNH 2 + ions, [Sb 6 O 10 Cl 14 ] 4- ions, in which the central unit is a Sb 4 O 6 skeleton with a double heterocubane-like arrangement with two missing corners, and of in­ cluded acetonitrile molecules without bonding interactions.

Cu 6 Br 6 (NPMe 3 ) 4 has been prepared as a by-product from the reaction of CuBr with Me 3 SiNPMe 3 in a CH 2 Cl 2 suspension. The dark red-violet crystals, which contain three molecules CH 2 Cl 2 per unit cell, have been characterized by a crystal structure determination. Cu 6 Br 6 (NPMe 3 ) 4 · 3 CH 2 Cl 2 : Space group P1̅, Z = 2, lattice dimensions at -95 °C: a = 1165.2(4), b = 1168.9(4), c = 1842.9(6) pm, a = 75.61(3)°, β = 84.15(3)°, γ = 61.08(2)°, 6918 observed unique reflections, R = 0.066. In the cluster molecule Cu 6 Br 6 (NPMe 3 ) 4 the copper atoms form a nearly ideal octahedron with Cu-Cu bond lengths of 268.8 pm in average. Each of the Cu atoms is con­nected with a terminal bromine atom. Four planes of the octahedron are capped by μ 3 -nitrogen atoms of the (NPMe 3 ) - groups.

A new by-product in the synthesis of ferroceno[1,2]cyclohexen-1-one-3 (1) is the dimer 2, which has been characterized by an X-ray analy­sis. Molecular structure of 2: Space group C 2h/6, C2/c, (15). Unit cell (Å): a = 42.54(3); b = 10.062(6); c = 22,04(1); monoclin; Z = 8.

Reaction of Rb 2 CO 3 with Te in Methanol at 160 °C in the presence of Ge yields the polytellu­ ride RbTe 6 , the structure of which has been deter­mined by X-ray structural analysis. The poly­anions 2 ∞ [Te 6 - ] contain Te 6 rings with a chair conformation, which are connected via four Te-Te bonds into a layer structure. A T structure is exhibited by the resulting TeTe 3 units. The Rb cations adopt positions between neighbouring parallel anion layers and are surrounded by 12 Te atoms in their first coordination sphere.