Volume 33, Issue 12

The preparation and spectroscopic characterization of thiocarbonyl metalloporphyrins M(OEP)CS(L') (e.g. 2e: M = Fe, L' = Py, 1e: M = Os, L' = Py** are described. Especially noteworthy is the existence of a pentacoordinate, diamagnetic, air-stable heme Fe(OEP)CS (2f: M = Fe, no L′). A linear correlation of the α-band frequencies (expressed as ϋ a ) in the optical spectrum and the metal(II/III) redox potentials (E 1/2 ) taken from cyclic voltam­metry experiments suggests (Abb. 3) that in complexes of the type M(OEP)LL' (1,2) λ a is bathochromically shifted as the π-acceptor capacity of L increases (“Rule of Bathochromism”). The strong π-acceptor capacity of carbon monosulphide renders the attack of dioxygen to the thiocarbonyl heme unfavourable; O 2 and CS seem to be comparable in their π-acceptor strength.

Reduction of anhydrous nickel(II) compounds in the presence of diazadienes RN=CR'-CR' = NR, |(DAD), yields (DAD) 2 Ni(0). This complex 1 with R = CH(i-C 3 H 7 ) 2 is especially reactive and comproportionates with DADNiBr 2 (2) to yield the bromobridged dimeric nickel(I) species (DADNiBr) 2 (3). The crystal and molecular structure of 3 has been determined by single crystal X-ray diffraction: Space group Pbca with a = 1225.8(12), b = 1474.8(14) and c = 2167.4(22) pm; Ra = 0.076, 1034 reflections. Catalytic tetramerisation of substituted alkynes with 1 is discussed in view of the very easy formation of dimers 3.

The organocyclotriarsane, CH 3 C(CH 2 As) 3 (1), reacts with chromium hexacarbonyl on ultraviolet irradiation to give the complex CH 3 C(CH 2 As) 3 Cr(CO) 5 (2), in which the cyclo-triarsane is behaving as a monodentate ligand. The crystal structure of 2 has been determinated by X-ray diffraction. The monoclinic unit cell (space group P2 1 /n) contains 4 isolated molecules in a hexagonal closest packing. The mass spectrum of 2 shows the parent peak and clear fragmentation patterns. The infrared and Raman spectra are reported for 1 and 2 in the 3000-30 cm -1 region. Most of the fundamental vibrations are assigned.

The first two examples of a novel series of organo-actinide complexes, [Cp 3 UXL] (Cp = η 5 -C 5 H 5 , X = halide or pseudohalide anion, L = uncharged Lewis base), are described. The X-ray structure analysis of the system with X = NCS and L = CH 3 CN confirms an almost linear alignment (H 3 )CCNUNCS along with the coplanarity of the three Cp ring normals. The remarkable Lewis acidity of certain Cp 3 UX-compounds appears to be essential for the formation of oligomeric species [Cp 3 UX] ∞ as well as for specific reactions of monomeric CP 3 UX.

On reaction of (C 5 H 5 )MoCl 2 (1) with equivalent amounts of Na 2 S 2 in ethanol, (C 5 H 5 ) 2 MoS 2 (2) is formed together with (C 5 H 5 ) 2 MoS 4 (3) and separated from 3 by vacuum sublimation. The more stable tetrasulfide 3 is obtained as the main product from 1 or 2 with excess Na 2 S 2 and also from 2 or (C 5 H 5 ) 2 Mo(SH) 2 (4) with S 8 in chloroform. A threemembered ring chelate structure involving side-on bonded S 2 2- ligands and pseudotetrahedrally coordinated Mo +4 central atoms is postulated for 2.

Cp(CO) 2 Fe-4,4,5,5-tetramethyl-1,3,2-dioxarsolane (1) is prepared from 2-chloro-dioxarsolane and Na[Fe(CO) 2 Cp]. 1 reacts with THF · Cr(CO) 5 to yield the hetero dinuclear compound (2) and is easily converted into Cp(CO) 2 Fe-AsCl 2 (3) by reaction with CH 3 C(O)Cl. 1 and 3 exhibit four υCO absorption bands instead of the two predicted. υCO doubling is attributed to the first examples of conformational isomerism about the arsenic-iron bond. Assignment of the CO stretching frequencies to the separate conformers is achieved by use of the 13 CO satellite bands.

1,3,4,5-Tetraethyl-2-methyl-1,3-diborolene (5) reacts with nickelocene and dimeric cyclopentadienylcarbonylnickel, yielding orange red 4 a, a diamagnetic nickelocene analogue. 1 H and 11 B NMR data indicate a sandwich structure, which is confirmed by X-ray structure analysis. The title compound crystallizes in the space group Pnma with a = 9.265(I), b = 15.1343(9), c = 12.777(2) Å and four molecules in the unit cell. All metal carbon distances are similar to those of the isoelectronic ferrocene.

S-Trifluoromethyl sulfurmonofluoride imides (R = CF 3 CO (1), NC (2), (CF 3 ) 2 CF (3), C 2 F 5 (4)) are prepared by the reaction of CF 3 SF 3 with appropriate nitrogen derivatives; from cyanuric fluoride and CF 3 SF 3 the S(+2) derivative (CF 3 ) 2 N-SCF 3 (5b) is formed. In (3) and (4) fluorine is substituted by N-silylated amines and PCl 5 to give (7) respectively. Silver pseudohalides AgX (X = NCO, NCS) will exchange the chlorine in 7.

Trifluorovinyl substituted phosphanes have been synthetized by reactions of halogenated phosphanes and trifluorovinyllithium. Some reactions of diphenyltrifluorovinylphosphane have been investigated and 31 P as well as 19 F NMR spectra have been measured. 19 FNMR data - shifts and coupling constants - have been calculated for comparison with measured spectra.

Varius products of the reaction of tris(trifluorovinyl)phosphane with organic lithium reagents have been isolated either while preparing tris(trifluorovinyl)phosphane or by special synthesis. 31 P, 19 F NMR and mass spectra, although complex, have been used for identification of compounds.

The isotypic compounds CaRh 2 B 2 and CaIr 2 B 2 were prepared and investigated by X-ray methods. They crystallize orthorhombic in space group Fddd-D 2h 24 with lattice constants CaRh 2 B 2 : a = 1060.6 ± 0.4 pm, b = 924.0 ± 0.4 pm, c = 583.2 ± 0.2 pm. CaIr 2 B 2 : a = 1072.7 ± 0.4 pm, b = 925.7 ± 0.4 pm, c = 587.7 ± 0.2 pm. The structure contains isolated boron-atoms and can be derived from the CeCo 3 B 2 - or CaCu 5 -type of structure, respectively.

Li 2 In crystallizes isotypic with Li 2 Ga, space group Cmcm-D 2a 17 , a = 476.3(1), b = 1001.7(3) and c = 473.5(1) pm, the In-atoms build up zig-zag-chains. Li 13 In 3 forms a new structure type, f.c.c., space group Fd 3m-O h 7 , a = 1355.6(2) pm; it can be described as an ordered variant of the b.c.c. package with isolated In-atoms.

Lithium-2-methylmercaptobenzol-1-thiolat reacts with C 5 H 5 Fe(CO) 2 Cl to give [C 5 H 5 Fe(CO) 2 (S-C 6 H 4 -SCH 3 ]); with C 5 H 5 Mo(CO) 3 Cl cleavage of metal chlorine and metal carbonyl bonds occurs yielding [C 5 H 5 Mo(CO) 2 (S-C 6 H 4 -SCH 3 )]. Reaction of dilithium- benzene-1,2-dithiolate with C 5 H 5 Fe(CO) 2 Cl leads to the binuclear [{C 5 H 5 Fe(CO) 2 } 2 S 2 C 6 H 4 ]. CO substitution and rearrangement are observed on irradiation of the complexes yielding [μ-S 2 C 6 H 4 {C 5 H 5 Fe(CO)} 2 ], [C 5 H 5 Fe(CO)(S-C 6 H 4 -SCH 3 )] and [C 5 H 5 Fe(μ-S 2 C 6 H 4 )] 2 . Syn­theses, properties and spectra of the complexes are reported and discussed.

CH 3 NH 3 PbX 3 (X = Cl, Br, I) has the cubic perovskite structure with the unit cell parameters a = 5,68 Å (X = Cl), a = 5,92 A (X = Br) and a = 6,27 A (X = I). With exception of CH 3 NH 3 PbCl 3 the compounds show intense colour, but there is no significant conductivity under normal conditions. The properties of the system are explained by a "p-resonance-bonding". The synthesis is described.

The preparation and properties of the new compounds [I(2,4 lutidine) 2 ]NO 3 , -ClO 4 , [I(2,6 lutidine) 2 ]NO 3 , -ClO 4 , [I(2,4,6 collidine) 2 ]NO 3 , -ClO 4 , [I(TEDA) 2 ]NO 3 , [I(quinu-clidine) 2 ]SbCl 6 , quinuclidine · IBr, quinuclidine · ICl, quinuclidine · IClSbCl 5 , TEDA · I 2 , I 2 · TEDA · I 2 , and ClI · TEDA · ICl are reported. The molecular vibrations and force constants are compared to those of similar compounds previously prepared.

Tri(tert<-butyl)phosphine imine has been prepared by desilylation of the corresponding N-trimethylsilyl compound. The imine, which is stable against water, oxygen, sodium, and lithium hydride, can be protonated by hydrogen halides, methylated by methyl iodide, and lithiated by lithium methyl. The pyrolysis at about 200 °C leads to tri(tert-butyl)- phosphine. From N-lithium tri(tert-butyl)phosphine imide N-substituted derivatives can be obtained.

The bifunctional acylphosphanes RC(O)P(Ph)-(CH 2 ) 2 -(Ph)PC(O)R (1 a-c) [R = CH 3 (a), CF 3 (b), C 5 H 6 (c)] are obtained from [NaP(Ph)CH 2 -] 2 and the corresponding acid chlorides RC(O)Cl. Etherical solutions of 1 a-c with molecular oxygen easily can be transformed into the dioxides [RC(O)P(O)(Ph)CH 2 -] 2 (2a-c). In contrast to the monofunctional acyl(diaryl)phosphane oxides 2 a-c do not react with water at 25 °C. The 31 P, 19 F, 1 H NMR and IR spectra of the new compounds 1, 2 a-c are discussed.

Besides the well-known argyrodite (Ag 8 GeS 6 ), the new compound Ag 2 GeS 3 could be synthesized from Ag 2 S-GeS 2 mixtures. Ag 2 GeS 3 crystallizes in an orthorhombic variant of the Wurtzite structure. Treatment of Ag 2 GeS 3 in a AgI/AgCl-eutectic yields the quaternary compound Ag 7 GeS 5 I. Crystal data for Ag 7 GeS 5 I and some analogous compounds are given.

Tri-tert-butylchlorosilane reacts with potassium pseudohalides in the presence of catalytic amounts of the crown ether 18-crown-6 to give the tri-tert-butylsilicon pseudo-halides (t-C 4 H 9 ) 3 SiX (X = CN, NCO, NCS, N 3 ) in good yields. These new compounds are characterized by IR, 1 H NMR, and mass spectra. In the absence of the crown ether no reaction occurs. Treating tri-tert-butylsilane with AgX (X = CN, SCN) gives the silicon pseudohalides in low yields.

Tri-tert-butylsiloxane compounds of transition metals are obtained by two different routes, one of these involves condensation of tri-tert-butylsilanol with the binary oxides V 2 O 5 , CrO 3 , MoO 3 , and Re 2 O 7 , while the other proceeds via a similar reaction between the chlorides VOCl 3 , NbCl 5 , TaCl 5 , CrO 2 Cl 2 , and the silanol. The new compounds, having good thermal stability and remarkable resistence to hydrolysis, are characterized by IR, 1 H NMR, and mass spectra.

N(CH 3 ) 4 [BCl 3 N 3 ], N(CH 3 ) 4 [AlCl 3 N 3 ], K[BCl 3 NCO] and K[AlCl 3 NCO] were prepared from N(CH 3 ) 4 N 3 and KNCO with BCl 3 and AlCl 3 using liquid SO 2 as solvent. It is essential to avoid any excess of the halide in order to supress secondary reactions. The IR spectra show the NCO group to be bonded via its nitrogen atom.

Bromo-Elpasolites of formulae Cs 2 LiMBr 6 and Cs 2 NaMBr 6 (M = Sc, Y, La-Lu, In, V, Cr) were prepared and investigated by powder X-ray diffraction. The compounds Cs 2 NaMBr 6 (M = Ce-Lu, Sc, Y, In) as well as Cs 2 LiMBr 6 (M = La-Er, Y) crystallize cubic facecentered (elpasolite type of structure); Cs 2 NaLaBr 6 and low temperature forms of Cs 2 NaMBr 6 (M = Ce-Gd) are tetragonal. Several hexagonal crystal structure types (HT-K 2 LiAlF6, Cs 2 NaCrF 6 , Cs 2 LiGaF 6 ) are observed for Cs 2 LiMBr 6 (M = Tm, Yb, Lu, Sc, In, V, Cr).

The specific rate constants for the acid-catalysed hydrolysis of ethyl hydrogen succinate in water and in a series of acetone-water and dioxane-water mixtures were determined at 30-45 °C. The solvent composition covered the range 0-90% by weight of the organic solvent. The rate was found to decrease to a minimum at about 80% of the organic solvent then to increase again with successive addition of the latter. In dioxane-water medium a slight initial increase in rate on the first addition of dioxane to water was observed and attributed to an increase in the number of "free" water molecules. The activation energy showed only slight dependence on solvent composition. The radius of the activated complex was calculated in the two media. The thermodynamic parameters were evaluated and discussed in terms of solvent composition. The reaction proved to be essentially an ion-dipole rather than an ion-ion interaction. A comparative discussion of the specific solvent effects of the two solvent systems under consideration is presented, based on the respective bond energies as given by the heats of mixing of the solvent components.

Cobalt(II)-hexacyanoferrates(II) with incorporated monovalent Na + , K + , NH 4 + and Cs + ions have been synthetized. Chemical composition and structure of the unit cell of the crystallites have been determined by X-ray and IR analysis. It has been found that all crystallites containing the monovalent cations are isomorphous having an FCC structure, whereas the cobalt(II)-hexacyanoferrate(II) crystallites tetragonally. In order to explain the properties of these crystallites (which are similar to zeolites) causing their selectivity to monovalent cations, a structure model has been proposed. The values of effective radii of the "cages" and their entrances have been calculated.

59 Co NMR chemical shifts are reported for complexes of the type [(CH 3 ) 3 M] n [ t C 4 H 9 ] 3-n P(CO)-2(NO)Co (M = Si, Ge, Sn; n = 1, 2, 3) and related to some IR and UV spectral data of the same compounds.

The synthesis of visnaginone-oxime (2 a) and khellinone-oxime (2 b) is reported. Beckmann rearrangement of 2 a and 2b using different cyclising agents was studied. Structure assignement for the produced benzoxazole derivatives and benzisoxazole derivatives was confirmed by chemical and spectral evidences. Utilization of visnaginone (la) and khellinone (lb) for the synthesis of new furoflavone derivatives was also undertaken.

Rates of HCN elimination from polycyanides N,N-dimethyl-4-(1,2,2-tricyanoethyl)-aniline (1), 9-cyano-9-dicyanomethyl fluorene (2), 1,1-diphenyl-1,2,2-tricyanoethane (3), and 2-phenyl-1,1,2-tricyanopropane (4) have been studied in methanol. Elimination from 1 occurs via (E 1 c B) R , mechanism. On the other hand olefin formation from 2-4 has been shown to occur via (E 1) anion pathway. Heavy atom kinetic isotope effects indicated that product stability is not the sole factor controlling the transition state geometries. Values of k 12 /k 14 were found to be in the order 2 > 3 > 4 > 1 which implied transition states with more carbanion-like structure in the opposite direction. Solvent isotope effects and enthalpies of activation were also determined and discussed in terms of transition states geometries.

The synthesis of 6-(4-methoxyphenyl)-5-phenyl-3-oxo-2,3-dihydro-1,2,4-triazine (5a) from 4-methoxybenzoin, 4-methoxybenzil, or 4-methoxybenzoin semicarbazone and semi-carbazide hydrochloride is reported. The condensation of 4-methoxybenzil with thiosemi-carbazide yielded 6-(4-methoxyphenyl)-5-phenyl-3-thioxo-2,3-dihydro-I,2,4-triazine (5b) which was converted to its 3-oxo analogue 5 a with acetic anhydride. Reduction of 5 a and 5 b with zinc and aqueous acetic acid led to the corresponding 2,3,4,5-tetrahydro-1,2,4-triazines 6 a and 6b, respectively. Oxidation of 5 b with iodine in sodium carbonate solution afforded bis [6-(4-methoxyphenyl)-5-phenyl-1,2,4-triazin-3-yl]disulphide (7). Analogous triazines were prepared by condensing 3,3'-diiodobenzil with semicarbazide hydrochloride or thiosemicarbazide.

Ferrocenealdehyde have been condensed with some amines giving the corresponding Schiff bases. Cyclocondensation reaction of chloroacetylchloride (or thioglycolic acid) on ferrocenyl Schiff bases yielded ferrocenyl-β-lactams and ferrocenylthiazolidinones.

The synthesis of spiro-γ-amino(or γ-chloro)-β lactams and spiro-4-thiazolidones by the cycloaddition reaction of 3-isatylidene anil derivatives, phthalylglycyl chloride (or chloroacetyl chloride) and/or mercaptoacetic acid has been investigated. 3-Isatylidene anils were prepared by the reaction of isatine with substituted aniline, a-naphthylamine, 2-aminothiazoles, 2-aminothiadiazoles and 2-aminopyridine, respectively.

Carbocations of the tri-phenylmethylseries give with I n - salts which are characterized by the natur of the anion. The preparation and general physical, spectral and chemical properties of tris-(4-dimethylaminophenyl)-carbenium-triiodid (1), a salt of crystal violet, and bis-(4-dimethylaminophenyl)-phenyl-carbenium-triiodid (2), a salt of malachite green, are described. The structure of the cations and anions of these carbeniumsalts is determined from their spectral data.

Tris-(4-dimethylaminophenyl)-carbenium-triiodid, a salt of crystal violet, is determined as probable structure of the Gram Staining of Bacteria. A mechanism of it is proposed based on the chemical properties of this salt.

A series of benzoylacetaldehyde benzoylhydrazones were prepared and characterised. Their UV, IR, and 1 H NMR spectra suggest the enol-imine structure rather than the keto-imine form of analogous Schiff bases. The pK a values of these aroylhydrazones were also measured and correlated with the Hammet substitution constants. Attempted cyclizations of these open-chain aroylhydrazones afforded the corresponding 5-hydroxy-2-pyrazoline compounds rather than the expected pyrazoles.

True carvone hydrosulphide has been prepared and its CD and ORD spectra examined. The spectra of another product from the reaction of carvone and hydrogen sulphide, which is probably a bi-cyclic thiane, have also been recorded.

1,2,3-Trioxo-2,3,6,7-tetrahydro-1 H,5H-benzo [ij] quinolizine (I) does not react with 2-aminopyridine to give a Schiff base [2], but reacts by ringcontraction to the spiroindolone 1/I, which can be hydrolysed to 1-(2-pyridyl-amino)1,2,5,6-tetrahydro-4 Hpyrrolo[ 3,2,1-ij]quinoline-2-one (2/1). In the same way the reaction of I resp. 1-phenylquinolinetrione (II) with tert-butylamine in aliphatic alcohols yields by ringcontraction the indolone acid esters 5 a-c. Reaction of I with tert-butylamine without solvent forms the ringcontracted amide 5c/I.

Reappraisal of the 13 C NMR data for mulberrin and mulberrochromene indicate a revision of structure for these two compounds as well as for cyclomulberrin and cyclo-mulberrochromene .

The combined action of triethyl orthoformate and aniline upon Meldrum's acid or 5-aza-5-phenyl-1-oxaspiro[5,5]undecan-2,4-diones gives their anilinomethylene derivatives (2, 5), which react with methyleneactive nitriles in dimethylformamide to give substituted 2-hydroxy-6-oxo-1,6-dihydro-pyridines (7) in excellent yields.

A low temperature (-90 °C) X-ray structural analysis of S 6 single crystals yielded improved data for the bond distances (206.8 pm), bond angles (102.6°), and torsion angles (73.8°) of the D3d molecule which are in agreement with current theories of homonuclear sulfur bonds.

Tri(tert-butyl)phosphine Oxide, Imine, Methylene, Borane Tri(tert-butyl)phosphine oxide, imine, methylene and borane have been prepared and their properties investigated. The imine is chemically inert due to strong steric hindrance. Its thermal decomposition at 200 °C leads to tri(tert-butyl)-pliosphine, in contrast to the methylene analogue which undergoes reductive elimination of isobutene. Both the oxide and borane are thermally very stable (> 250 °C).

The metallation of η 5 -C 5 H 5 Mn(CO) 2 PH 3 with excess n-butyllithium and consecutive reactions with CH 3 I and (CH 3 ) 3 SiCl yield the complexes η 5 -C 5 H 5 Mn(CO) 2 PR 3 (R = CH 3 , Si(CH 3 ) 3 ). The product of the lithiation is proposed to be η 5 -C 5 H 5 Mn(CO) 2 PLi 3 .

Unlike chlorination fluorination of ammine complexes of platinum(IV) in aqueous solution does not lead to haloamido complexes. Instead, the triammine complexes [Pt(NH 3 ) 3 Cl 3 ]Cl and [Pt(NH 3 ) 3 (NCl 2 ) 2 Cl]Cl yield no definite main product, and the tetrammine and pentammine complexes trans-[Pt(NH 3 ) 4 Cl 2 ]Cl 2 , [Pt(NH 3 ) 4 (NCl 2 )Cl]Cl 2 , [Pt(NH 3 ) 5 Cl]Cl 3 , and [Pt(NH 3 ) 5 (OH)]Cl 3 form the sparingly soluble complex trans -[Pt (NH 3 ) 4 Cl 2 ](H 2 F 3 ) 2 · 2H 2 O as the main product.

Photoreactions of 2-exo-bromo-5,6,7,8,9,9- hexachloro-1,2,4 a, 5,8,8 a-hexahydro-5,8-methanonaphthaline (1) were studied in the presence of acetophenone. With the help of column chromatography an unusual isomerisation product (3) was isolated, whose structure was established by spectral data obtained by mass spectrometry, infrared spectroscopy, and 1 H nuclear magnetic resonance measurements.