Band 45, Heft 4

WCl 6 reacts with two equivalents of tellurium in a sealed evacuated ampoule in the temperature range from 170 to 190 °C to give Te 4 2+ (WCl 6 - ) 2 . Under the same conditions with one equivalent of tellurium WCl 5 yields Te 4 2+ (WCl 6 - ) 2 and WCl 4 . Te 4 (WCl 6 ), formes black crystals, which are sensitive to moist air. It decomposes at temperatures above 300° C to Te and WCl 6 . The crystal structure determination (lattice constants a = 638.9(1), b = 753.2(2), c = 1102.0(5) pm, α = 101.19(2)°, β = 102.85(2)°, γ = 90.21(1)°, Z = 1, triclinic space group P 1̄, 3572 unique reflections for 82 parameters, final R = 0.026) shows the nearly ideal square Te 4 2+ cation with Te–Te distances of 268.8 and 268.7 pm and markedly distorted WCl 6 – octaedra with W–Cl bond length from 227.5 to 237.3 pm. The structure involves interionic Te–Cl contacts as short as 319 pm.

The structure of the first of the new alkali metal chalcogenides of the composition M 5 X 3 has been solved (K 5 Te 3 : a = 13.742(2)Å, c = 6.364(2) Å, space group: I 4/m, Z = 4). It can be derived from the W 5 Si 3 type of structure by substituting the · · · Si · · · Si · · · Si · · · chains by those of Te 2 2- -dumbbells · · · (Te–Te) · · · (Te–Te) · · · (Te–Te) · · · , both running along [001]. The Te 2 2- -dumbbells occur as a consequence of the necessity of charge compensation of the saltlike compound K 5 Te 3 , according to 2 K 5 Te 3 ⇌ 10 K + + Te 2 2- + 4 Te 2- . The remaining tellurium atoms not involved in the dumbbells build up strings of tetrahedra ∞ 1 [ΚΤe 4/2 ], with common edges along [001]. Therefore, the resulting K–K distances in these strings of tetrahedra are extremely short (3.18 A).

Cp*NbF 4 (1) (Cp* = η 5 -C 5 Me 5 ) reacts with lithium salts of β-diketones under elimination of LiF to form the chelate complexes (2) and (3). The X-ray crystal structure of 3 was investigated and is compared with the homologous tantalum compound.

[CH 3 CN—WCl 4 (NSeMe)] and [PPh 3 Me][Cl 5 W(NSeMe)] have been prepared by the reaction of Me 3 SiSeMe with [CH 3 CN—WCl 4 (NCl)] and [PPh 3 Me][WCl 5 (NCl)], respectively, as brown, moisture sensitive crystals which were characterized by IR spectroscopy. The crystal structure of [PPh 3 Me][Cl 5 W(NSeMe)] was determined: Space group PĪ, Z = 4, 7599 observed unique reflexions, R = 0.046. Lattice dimensions at —70°C: α = 1104.6(6), b = 1489.2(9), c = 1650.6(8) pm, α = 108.37(4)°, β = 90.71(4)°, γ = 93.83(4)°. The compound forms ions [PPh 3 Me] + and [Cl 5 W(NSeMe)] - , in which the tungsten atoms is octahedrally coordinated by five chlorine atoms and by the nitrogen atom of the (NSeMe) 2- ligand. The bond lengths WN 171.6(8), NSe 180.6(9) pm and bond angles WNSe 173.6(7)°, NSeC 98.3(5)° (in average of the two independent anions) are in agreement with the proposed formula W ≡ N—Se—Me ↔W = N = Se—Me.

The reaction of two equivalents of Me 3 Si—N=PPh 2 N=S(O)Me 2 (1) with SeOCl 2 proceeds with elimination of (Me 3 Si) 2 O to yield SeCl 2 [N=PPh 2 N=S(O)Me 2 ] 2 (2) as a white powder. Crystals of 2 that are suitable for X-ray crystal structure analysis have been obtained by recrystallization from acetonitrile. The structure of 2 shows very short selenium-nitrogen bonds.

The organoboration of bis(alkynyl)plumbanes (1) leads to intermediates 7 in which a triorganolead cation is stabilized by intramolecular side-on coordination to the C=C triple bond of an alkynylborate function. These compounds decompose rapidly at room temperature or rearrange to give 1,4-plumbabora-2,5-cyclohexadienes (10). If the compounds 7 are treated with an excess of trialkylborane (2) they are converted into bis(alkenyl)lead derivatives (8) as the final products (8c, 8ca) or again as intermediates for the 2,5-bis(dialkylboryl)-3-plumbolenes 9. A mechanism suggested for the formation of 9 is based on the product distribution (9ab/9ba = 2:1) obtained from the reaction of a distinct compound 7a with different trialkylboranes (2a, 2b). All compounds have been fully characterized by multinuclear magnetic resonance data ( 1 H, 11 B, 13 C, 207 Pb), dynamic NMR and two-dimensional (2 D) NMR techniques. In addition, these techniques have been applied to some of the analogous tin compounds (e.g. 4b, 5).

The reaction of cis-Fe(CO) 4 Br, with ferrocenyl lithium, FcLi, leads to the binuclear a hexacarbonyldiiron complexes Fe 2 ,(CO) 6 (μ-Br)(μ-CFc) (7), Fe,(CO) 6 (μ-COFc) 2 (8) and Fe 2 (CO) 6 (μ-C 2 Fc 2 O) (9) b . Addition of FcLi to Fe(CO) 5 gives the ferrocenoyl tetracarbonylferrate anion which was characterized as the salt NEt 4 + [Fe(CO) 4 (FcCO)] - (10); 9 is obtained after reaction of the anion with Meerwein’s salt, Me 3 O + BF 4 - . The reaction of Fe 2 (CO) 9 with FcLi, followed by methylation with Me 3 O + BF 4 - , results in the formation of Fe 2 (CO) 8 [μ 2 -C(OMe)Fc] (11) which can be extracted from the product mixture using pentane. Chromatography of the product mixture over silica, however, leads preferentially to the formation of trinuclear a complexes of the type Fe 3 (CO) 9 (μ 3 -COMe)(μ 3 -CR) (R = Fc (12), OMe (13) and O(CH 2 ) 4 OMe (14)) in addition to 9; the same products are obtained starting from Fe 3 (CO) 12 . No complexes could be isolated which contained a direct iron σ-ferrocenyl bond. The structures of the new complexes were deduced from their infrared, mass, 1 H and 13 C NMR spectra. The bis(ferrocenoyl)-bridged compound 8 was also characterized by an X-ray crystallographic structure analysis.

Hexachlorocyclotriphosphazene (Cl 2 P=N) 3 reacts with hydrazine or dihydrazidophosphoric acid O-phenyl-ester in THF in the presence of triethylamine to give the spirocyclic title compounds. Constitutions are confirmed by MS, NMR and IR spectra. { 1 H} 31 P NMR spectra at 36.23 MHz are of higher order – ABCD and A 2 BB′A′ 2 – and can be simulated with the appropriate shifts and coupling constants.

The cubane-type diamagnetic cluster Mo 3 SnS 4 (Et 2 PS 2 ) 6 (1) is obtained by reaction of the “incomplete” cubane Mo 3 S 4 (Et 2 PS 2 ) 4 either with tin powder and Et 2 P(S)—S—S—P(S)Et 2 or with bis(diethyldithiophosphinato)tin(II). While the Sn atom and two of the Mo atoms in the core are chelated by Et 2 PS 2 ⁻, the remaining Mo atom serves as a bridgehead for three dithiophosphinato-ligand bridges to the other metals. 1 crystallizes in the orthorhombic space group Pbca with Z = 8 and lattice parameters a = 2240( 1), b = 2261 ( 1), c = 2401 (1) pm.

Nd 2 SeSiO 4 has been prepared as violet rod-like single crystals by reaction of elemental neodymium, selenium and iodine in the ratio 1.0:1.0:2.5 and subsequent reaction with quartz glass powder. The compound crystallizes in the orthorhombic space group Pbcm with a = 618.2(2), b = 717.4(2), c = 1102.4(2) pm and Z = 4. The structure is built up of alternating NdSe- and NdSiO 4 -sheets.

The dark blue title compound has been prepared by reaction of [Re,Cl 8 ] 2- and F-, both dissolved as ion pairs with [(n–C 4 H 9 ) 4 N] + in anhydrous CH 2 Cl 2 , and recrystallization from acetone/diethylether. Structure determination by single crystal X-ray diffractometry at 150 K reveals crystallization in the cubic system, space group Pn3̄n with a = 19.783(3)Å, V = 7742.4Å 3 , Z = 6. The {[Re 2 F 8 ]·O(C,H 5 ) 2 } 2- entity consists of an axially elongated F 8 -cubane frame around the Re, unit, which is coordinated at one side by an ether molecule (Re–O distance 2.64(4)Å) and displaced from the center towards the ether. The Re– Re quadruple bond (2.188(3)A) is the shortest of the four octahalogenodirhenates(III). In contrast to its Cl, Br and I homologues no disorder of the Re, units is observed. The Re– F distances of 1.92(3) and 1.96(3)A are equal within the standard error, and the Re–Re–F angles are 99.9(4) ⚪ and 102.6(4) , respectively. The UV-Vis spectrum of [(n–C 4 H 9 ) 4 N] 2 [Re 2 F 8 ] shows only the δ-δ* transition at 558 nm (ε = 771 cm 2 /mmol). At 10 K this band exhibits a weak vibrational fine structure with an averaged progression of 209 cm -1 . The Raman spectrum is dominated by v(Re–Re) at 317.5 cm -1 with up to five overtones, the IR spectrum by v(Re–F) at 560 cm -1 . Additional bands for the solvated compound at 525 and 306 cm -1 are assigned to v(Re–O) and v(Re–Re), respectively. The 19 F NMR spectrum in aceton-d 6 shows a singlet at –135.06 ppm; in the presence of ether an additional weak signal arises at –134.15 ppm versus external CFC1 3 .

The crystal structure of Me 3 SiNPPh 2 CH 2 PPh 2 (1) has been determined in order to obtain information about the ground state conformation in the solid, and about unusual steric effects which could give rise to conformational isomers. It was recently proposed that such isomers exist due to restricted rotation about the P=N bond, and are generated by heating the compound to 160 C. The evidence for them was based on the observation of multiple NMR signals in CDCl 3 solutions of samples which had been so treated. The crystal structure yields a P–N–Si bond angle of 150.2(2), a P–N bond length of 1.529(3) Å and a Si–N bond lengths of 1.668(3) A. It is clear that, as a result of the relatively large P–N–Si angle in 1, there is no steric hindrance to rotation about the P–N bond in this molecule. Attempts to study the energetics of the proposed isomerization by recording the NMR spectra of heated samples showed that the previously reported multiple NMR signals are not generated in this way. However, such signals are generated at ambient temperature under various circumstances, for example in the course of the reaction of a CDCl 3 solution of 1 with methanol to produce HNPPh 2 CH 2 PPh 2 (2). The observation that it is not necessary to heat 1 in order to generate these signals makes their assignment to rotational isomers rather less likely. In the absence of a reproducible method of producing these signals in a pure sample, the existence of such isomers should be regarded as not yet proven.

Nitridophthalocyaninatomanganese(V), MnNPc(2–), has been prepared by oxidation of [Mn(OH) 2 ,Pc(2–)] - with chlorine in the presence of excess ammonia in dichloromethane as a chemically very stable, diamagnetic microcrystalline blue powder. The band at 1053 cm -1 in the infrared and resonance Raman spectra is assigned to v(Mn=N). The strong resonance enhancement of v(Mn=N) coincides with an electronic transition at 461 nm assigned to (N → Mn) electron transfer. The UV-VIS spectrum in 1-chloronaphthalene is compared with that of the MnNPc(2–)–H 2 SO 4 adduct and the phthalocyanine-π-cation radical [MnNPc(1–)] + .

From aqueous solutions of potassium dithiosquarate and bis(ethylenediamino)copper(II) sulfate the following compounds have been obtained: [Cu II (en) 2 ][Cu II (C 4 O 2 S 2 ) 2 ] (2) and [Cu II (en) 2 (H 2 O)] 2 [Cu 4 I (C 4 O 2 S 2 ) 4 ] · 2 H 2 O (3). Their structures have been determined: Crystal data, 2, monoclinic, space group C 2/c, a = 1914.5(6), b = 823.0(1), c = 1669.5(5) pm, β = 133.23(1)°, Ζ = 4; 1809 reflections, R = 0.024. 3, triclinic, a = 779.2(3), b = 958.7(4), c = 1478.8(4) pm, α = 82.34(3), β = 82.68(2), γ = 73.47(3)°, Ζ = 1; 3376 reflections, R = 0.045. 2 contains infinite chains of centrosymmetrical [Cu(en) 2 ] 2+ cations and bisphenoidal [Cu(C 4 O 2 S 2 ) 2 ] 2- anions. 2 shows ferromagnetic behaviour above 75 K. At lower temperatures antiferromagnetic coupling between the chains dominates. 3 contains isolated [Co(en) 2 H 2 O] 2+ cations and tetrameric [Cu(C 4 O 2 S 2 )] - anions. The anion consists of a chain of tetrahedrally and trigonally coordinated Cu(I) atoms with short Cu · · · Cu distances of 255.2( 1 ) and 257.9( 1 ) pm. The dithiosquarate ligands are stacked in pairs.

A series of novel Fe(II) and Co(II) complexes containing dithiophosphinate groups and neutral ligands with sulfur and oxygen donor functions was prepared in non-aqueous solutions. The reaction systems FeSO 4 /Na{S 2 P(p-C 6 H 4 Me) 2 } and CoCl 2 /Na{S 2 P(p-C 6 H 4 Me) 2 } in different organic solvents afford the mononuclear complexes [Fe{S 2 P(p-C 6 H 4 Me) 2 } 2 (MeOH) 2 ], [Fe{S 2 P(p-C 6 H 4 Me) 2 } 2 (THF),], [Fe{S 2 P(p-C 6 H 4 Me) 2 } 2 (THT) 2 ],[Fe{S,P(p-C 6 H 4 Me) 2 } 2 (DMF) 2 ], [Co {S 2 P(p-C 6 H 4 Me),},(DMF) 2 ] which were isolated as crystalline [Fe{S 2 P(p-C 6 H 4 Me) 2 } 2 (MeOH) 2 ]·2MeOH (1), [Fe{S,P(p-C 6 H 4 Me) 2 } 2 (THF) 2 ] (2), [Fe{S 2 P(p-C 6 H 4 Me) 2 } 2 (THT) 2 ]-THT (3), [Fe{S 2 P(p-C 6 H 4 Me) 2 } 2 (DMF) 2 ] · 2 DMF (4), and [Co{S 2 P(p-C 6 H 4 Me) 2 },(DMF) 2 ] · 2DMF (5), respectively. Crystals of 1 are monoclinic, space group P2 1 /c. Z – 2, a⁻ 11.013(3), b = 14.402(3), c = 11 600(3) Å. β = 106.25(2). The structure of 1 was refined to R(R η ) = 0.030 (0.040). Compound 2 is triclinic, space group P 1, Ζ = 1 with a = 6.921(2), b = 9.353(3), c = 14.436(4) Å, α = 83.56(3), β = 85.39(3) and γ = 80.46(2). Its structure was refined to R(R w ) = 0.029 (0.035). 3 crystallizes in the triclinic space group P l̄ with a = 9.204(3), b = 11.378(3), c = 11.389(4) Å α = 97.41(3), β = 114.00(2), γ = 100.69(2) and Ζ = 1. The refinement converged to R(R w ) = 0.057 (0.073). Crystals of 4 and 5 are monoclinic, space group P2 1 /n (Z = 2): Fe(II), a = 12.395(3), b = 11.077(2), c = 16.377(4) Å, β = 95.51(2); Co(II),α= 12.299(3), b = 11.055(2), c = 16.452(4) Å, β = 95.90(2). The refinements converged to R(R w ) = 0.045 (0.046) and 0.027 (0.033), respectively. The neutral complexes 1-5 contain six-coordinated metal centers with either MS 4 O 2 or MS 6 chromophores. They represent the first examples of structurally defined mononuclear Fe(II) and Co(II) complexes containing 1,1-dithiolate groups as well as additional neutral ligands with sulfur or oxygen donor functions.

[CpMo(CO) 3 ] 2 (1) (Cp = cyclopentadienyl) reacts with InCl 3 in diglyme to yield the oxo-cluster [Cp 3 Mo 3 (CO)4(μ-Cl)(μ 3 -O)] (2) and the cationic oxo-cluster [Cp 3 Mo 3 (μ-CO) 3 (CO) 3 (μ 3 -O)] + as the salt [Cp 3 Mo 3 (μ-CO) 3 (CO) 3 (μ3 -O)][CpMo(CO) 3 InCl 3 ] (3). The compounds were characterized by elemental analysis, spectroscopic data and X-ray structure analysis. Compound 2 crystallizes in the orthorhombic space group P2 1 2 1 2 1 with a = 1006.0(3), b = 1244.6(4) and c = 1600.8(5) pm, V = 2004.3 x 10 6 pm 3 , Z = 4. Compound 3 crystallizes in the monoclinic space group P 2 1 /m with a = 874.4(8), b = 1407(1) and c = 1500(1) pm, β = 92.95(6) , V = 1843 × 10 6 pm 3 , Z = 2.

Base catalyzed deglycosidation of elaiophylin leads to a reactive enone system. Following addition of thiols yield side-chain modified products of the title compound.

The reaction of ReCl 5 with a porphyrin H 2 (P) [2, 3] in refluxing trichlorobenzene represents a very efficient synthesis of oxorhenium(V) porphyrins ReO(P)X where X is a uninegative anion. Thus, rhenium is inserted to octaethylporphyrin and a variety of tetraarylporphyrins. The primary products are the paramagnetic trichlororhenium(V) porphyrins, ReCl 3 (P), which are remarkably resistant to hydrolysis. If moisture is not rigorously excluded from the metal insertion system, chlorooxorhenium(V) porphyrins ReO(P)Cl are formed which during alumina chromatography are converted to the methoxides ReO(P)OMe. All complexes ReO(P)X and ReCl 3 (P) are subject to alkaline hydrolysis yielding the μ-oxo complexes [ReO(P)] 2 O which are convenient starting materials for a variety of mononuclear species ReO(P)X [X = OMe, OEt, OiPr, OtBu, F, Cl, Br, OCIO 3 , OAc, OBz, OCN, NCS] on acidolysis with a number of monobasic inorganic and organic acids HX or reaction with alkali salts MX in presence of acetic acid. In the case of tetramesitylporphyrin, hydrolysis yields a mononuclear hydroxooxorhenium(V) porphyrin. The species ReCl 3 (P) and ReO(P)X are characterized by UV/VIS, IR, 1 H NMR and mass spectra.

The reaction of tris(2,4-pentanedionato)europium(III) with a porphyrin H 2 (P)** in boiling 1,2,4-trichlorobenzene affords a so-called “redox mixture” of europium(III) bisporphyrinates, i. e. porphyrin π-radicals of the type Eu(P) 2 and sandwiches EuH(P) 2 in which one of the porphyrin rings is protonated. Thus, from either tetraphenylporphyrin or its dilithium derivative, or octaethylporphyrin, or a mixture of both porphyrins, the corresponding mixtures of double-deckers with two identical or two differnt porphyrin rings are obtained. The transformation of the redox mixtures into the pure tetraphenylporphyrin derivatives Eu(TPP) 2 , EuH(TPP) 2 , and the salt [NBu 4 ] [Eu(TPP),, the separation of the octaethylporphyrin derivatives Eu(OEP) 2 and EuH(OEP) 2 , and the purification of the “mixed” double-decker Eu(OEP)-(TPP) are described. The compounds are characterized by cyclic voltammetry, IR, UV/VIS/NIR, 1 H NMR, and mass spectra. The obtained data indicate that the π-electrons of the two porphyrin rings behave as a common electronic system in which a defect electron is delocalized. However, in the “mixed” double-decker Eu(OEP) (TPP) the defect electron is more concentrated on the OEP ring, i. e. the porphyrin ring which is more easily oxidized.

The preparation, structure and spectral characteristics of intensely colored salts of 2-hydroxyimino-1,3-indandione with ammonia and amines are described. The crystallization of the salts takes place with a high yield. All the salts fluoresce in DMSO. MNDO calculations show that the formation of an anion from 2-hydroxyimino-1,3-indandione is associated with substantial alterations in the nitroso group.

Crystalline 3-O-acetyl-2,4-O-phenylboranediyl-β-D-ribopyranosyl bromide (5) is prepared by an easy four-step synthesis from D-ribose (1), the first three steps of which are realised in an one-pot manner. 5 reacts stereoselectively with sodium methoxide and phenoxide to give the pure methyl and phenyl a-D-ribopyranosides 7 a and 7 b after deboronation and deacetylation.

In addition to phenazine, phenazine-1-carboxylic acid, phenazine-1,6-dicarboxylic acid and 2,9-dihydroxyphenazine-1-carboxylic acid a new compound, viz. 2,3,9-trihydroxyphenazine-1-carboxylic acid could be isolated from the culture medium of Pseudomonas fluorescens grown under iron deficiency with beryllium added to the culture medium. Its structure elucidation is described.

Bis-alkoxy-disulfanes, ROSSOR, react with SCI, at 0 °C to give ROSSCl which yield the corresponding nonasulfanes, RO—S 9 —OR, on reaction with titanocene pentasulfide, (C 5 H 5 ) 2 TiS 5 . Raman, mass, and NMR spectra of ROSSCl and (RO) 2 S 9 (R = isopropyl) are reported.

The new compound Na 5 HfAs 3 crystallizes in a Na 5 SiP 3 type structure (monoclinic system, space group P2 1 /n (Nr. 14)) with the lattice constants: a = 1384.4(1) pm, b = 754.9(1) pm, c = 843.3(1) pm, β = 89.63(1)°. Two HfAs 4 -tetrahedra are connected by a common edge to form (Hf 2 As 6 ) 10- anions.

The title compound has been prepared by the reaction of 15-crown-5 with a solution of CoCl 2 in acetonitrile. It forms blue crystals, which were characterized by an X-ray structure determination. Space group Pca 2 1 , Z = 4, 2883 observed unique reflexions, R = 0.032. Lattice dimensions at –80 °C: a = 1420.9(3), b = 1017.2(2), c = 1775.0(3) pm. The lattice contains the complex ions [Co(15-crown-5)(CH 3 CN) 2 ] 2+ and CoCl 4 2- , and interstitial CH 3 CN molecules. In the cation Co II is seven-coordinate by the five oxygen atoms of the crown ether molecule and by two nitrogen atoms of the acetonitrile molecules in axial positions of a pentagonal bipyramide.

New tetranuclear iron(III) and manganese(III) complexes with 1,4-bis[N,N-bis(2-benzimidazolylmethyl)amino]butane, and their hexane derivatives were prepared. Magnetic measurements suggest that these have an oxo-bridged structure of Toftlund type.

1,1-Dichloro-3,5-diphenyl-4 H-1,2,4,6-λ4-selenatriazine