Volume 32, Issue 11

The following known and novel cobalt carbonyl complexes are formed by reactions of cobalt metal with bipy, phen, Ph 2 P-CH 2 -CH 2 -PPh 2 (P͡P), PPh 3 , Ph 2 P-CH 2 -CH 2 -NEt 2 (P͡N), InCl, SnX 2 (X = Cl, Br, I), Cd and HgBr 2 under CO pressure (200 bar): [Co(bipy) 3 ][Co(CO) 4 ] 2 , [Co(phen) 3 ][Co(CO) 4 ] 2 , [Co 2 (P͡P) 3 (CO) 4 ][Co(CO) 4 ] 2 ; Co 2 (CO) 6 (PPh 3 ) 2 , Co 2 (CO) 6 (P͡N) 2 ; [Co(CO) 4 ] 2 SnCl 2 , {[Co(CO) 4 ] 2 InCl} 2 ; [Co(CO) 3 PPh 3 ] 2 SnX 2 (X = Cl, Br, I), [Co(CO) 3 (P͡N)] 2 SnCl 2 , [Co(CO) 3 (P͡N)] 2 M (M = Cd, Hg).

By treatment of Co 2 (CO) 8 with 1-diphenylphosphino-2-diethylaminoethane, Ph 2 P-CH 2 -CH 2 -NEt 2 (P͡N), [Co(CO) 3 (P͡N) 2 ][Co(CO) 4 ] or Co 2 (CO) 6 (P͡N) 2 are formed, depending on the reaction conditions. The complex Co 2 (CO) 4 (nor-C 7 H 8 ) 2 also reacts with P͡N to give the substituted cobalt carbonyl Co 2 (CO) 6 (P͡N) 2 . Insertion of SnCl 2 and the II B group metals into the Co-Co bond is possible.

The anionic complexes [(olen)Fe(CO) 2 CN] - (olen=pentadiene-(1,3), hexadiene-(1,3), 2,3-dimethylbutadiene) and [M 2 (CO) 9 CN]- (M = Mn, Re) are formed by the reactions of (olen)Fe(CO) 3 or M 2 (CO) 10 (M = Mn, Re) with NaN[Si(CH 3 ) 3 ] 2 .

IR, Raman, and X-ray data of ZnSO 3 · 2½ H 2 O, ZnSO 3 · 2 H 2 O, ZnSO 3 ·½ H 2 O, ZnSO 3 , MnSO 3 · 3 H 2 O, MnSO 3 · H 2 O, MnSO 3 , MgSO 3 · 6 H 2 O, MgSO 3 · 3 H 2 O, CoSO 3 · 3 H 2 O, CoSO 3 · 2½ H 2 O, and CoSO 3 ·2 H 2 O are presented. Except of MgSO 3 ·6 H 2 O and ZnSO 3 · 2½ H 2 O the crystal structures of these compounds are yet unknown. The following crystal data could be determined by single crystal measurements: ZnSO 3 · 2 H 2 O (monoclinic, P2 1 /n) : a = 642.1, b = 852.4, c = 757.4 pm, β = 98.93°, Z = 4, MnSO 3 · 3 Η 2 Ο (monoclinic, Ρ2 1 /n) : a = 665.0, b = 890.6, c = 879.3 pm, ß = 96.11°, Z = 4, MnSO 3 · Η 2 Ο (orthorhombic) : a = 2565.1, b = 483.9, c = 576.0 pm, Z = 8, CoSO 3 · 3 Η 2 Ο (orthorhombic, Pna2 1 , isotype with MgSO 3 · 3 H 2 O): a = 952.7, b = 942.0, c = 552.1 pm, Z = 4, CoSO 3 • 2½ H 2 O (tetragonal) : a = b = 946.4, c = 1021.1 pm, Z = 8, CoSO 3 · 2 H 2 O (isotype with ZnSO 3 · 2 H 2 O) : a = 639.7, b = 855.3, c = 753.7 pm, β = 98.85°, Z = 4. The IR spectra show that with exception of MnSO 3 · H 2 O strong hydrogen bonds are present in the sulfite hydrates. The decomposition of the sulfites has been examined by thermal analysis. Dehydration of the sulfite hydrates starts at 90 (ZnSO 3 · 2½ H 2 O), 120 (ZnSO 3 · 2 H 2 O), 175 (ZnSO 3 · 1/2 H 2 O), 85 (MnSO 3 · 3 H 2 O), 205 (MnSO 3 · H 2 O), 70 (MgSO 3 · 6 H 2 O), 130 (MgSO 3 · 3 H 2 O), 120 (CoSO 3 · 3 H 2 O), 140 (CoSO 3 · 2½ H 2 O), and 150 °C (CoSO 3 · 2 H 2 O). Decomposition of the anhydrous sulfites occurs at 300-350 (ZnSO 3 ), 390-460 (MnSO 3 ), and 400-530 °C (MgSO 3 ).

By mixing aqueous solutions of Hg(CH 3 COO) 2 and KOCN the white precipitate K 2 Hg 3 (NCO) 8 is formed. When recrystallised from CH 3 OH colorless crystals of the compound KHg(NCO)3 are obtained. The crystal structure analysis (space group Pnma; α = 1015.2(6) pm, b = 399.3(3) pm, c = 1772.9(9) pm) shows a distorted KCdCl 3 arrangement with isolated Hg(NCO)2 molecules, K+ and NCO - ions. The vibrational spectra in the range of 250-3000 cm -1 are discussed. The rubidium compound is isotypous (a = 1019.0(6) pm, b = 411.6(4) pm, c = 1820.5(8) pm).

Tricyclohexyl-cyclotriphosphane, (c-C 6 H 11 P) 3 (1), is another relatively stable compound with a three membered phosphorus ring. It is produced in the reactions of (a) K 2 (c-C 6 H 11 P) 4 with CH 2 Cl 2 , (b) K 2 (c-C 6 H 11 P) 4 with CS 2 , (c) c-C 6 H 11 PCl 2 with sodium in dioxane. The following by-products are formed: (c-C 6 H 11 P) 4 CH 2 (3), (c-C 6 H 11 P) 5 (2) and (c-C 6 H 11 P) 4 in the reaction (a); mainly (c-C 6 H 11 P) 4 in the reaction (b); (c-C 6 H 11 P) 5 (2) and (c-C 6 H 11 P) 4 in the reaction (c). The P 3 ring compound 1 and the P 5 ring compound 2 can be isolated in a pure state. The oligomers (c-C 6 H 11 P) n , n = 3, 4, 5, clearly are distinguished by the melting points, the molecular masses and by the 31 P NMR and vibrational spectra. The 31 P NMR parameters of 3 are reported. The cyclohexyl groups in 1, 2 and 3 are situated on both sides of the corresponding ring systems, giving rise to a maximum number of “trans” orientated neighboring substituents.

The He (I) photoelectron spectra of the title compounds are described. The PE assignments are based on the comparison with the spectra of related compounds and on simple MO considerations (composite molecule–approach). The correlation between PE ionisation energies and molecular properties (e.g. SiP-(p→d)π-bonding) is discussed.

The reaction of MeOP(S)Cl 2 with N 2 H 5 OH leads to cis- and trans-3,6-dimethoxy-3,6-dithiocyclo-3,6-diphospha-1,2,4,5-tetrazane (1). The configurations of the products are assigned from comparisons of their Raman and IR spectra and from chromatographic and solubility data.

In contrast to tetranuclear bis(pentane-2,4-dionato)-cobalt(II), Co 4 (acac) 8 , which is cleaved by nitric oxide to give the adduct Co(acac)2(NO), the mononuclear tris(pentane-2,4-dionato)cobalt(III), Co(acac) 3 , is attacked by NO at the chelate ligands. The photonitrosylation of Co(acac) 8 in benzene or toluene solution leads to the oximato complex tris(3-hydroxyimino-pentane-2,4-dionato)cobalt.

Triphenylmethylene- and triphenylethylidenephosphorane react with h 5 -cyclopentadienyl-dicarbonylironiodide to yield the yellow stable complexes of the type [h 5 -C 5 H 5 Fe(CO)2-CHRP(C 6 H 5 ) 3 ]I (R = H (1), CH 3 (2)). By reaction of 1 and 2 with AgBF 4 the corresponding BF 4 -salts can be isolated. The new compounds are characterized by their 1 H NMR, 31 P NMR and IR spectra as well as by elemental analysis.

X-ray investigations of brown crystals, formed as a by-product in the reaction of Co 2 (CO) 8 with (C 6 H 5 ) 2 P(CH 2 ) 2 P(C 6 H 5 ) 2 show the existence of the complex Co 2 (µ-CO) 2 (CO) 4 μ-[(C 6 H 5 ) 2 P] 2 NH. The triclinic unit cell (space group PĪ ) contains two complex molecules and one molecule benzene as a solvate. The ligand (C 6 H 5 ) 2 P(CH 2 ) 2 P(C 6 H 5 ) 2 , prepared by literature methods, obviously sometimes contains some [(C 6 H 5 ) 2 P] 2 NH. The compound Co 2 (μ-CO) 2 (CO) 4 μ-[(C 6 H 5 ) 2 P] 2 NH can also be directly synthesized by the reaction of Co 2 (CO) 8 with [(C 6 H 5 ) 2 P] 2 NH.

The synthesis of (CO) 3 (η-C 5 H 5 )M—Co(CO) 4 and the cluster-compounds (CO) 9 Co 3 M(CO) 2 (η-C 5 H 5 ) (M = Mo, W) is described. IR, 1 H—NMR and mass spectroscopic data are discussed. The structure of (CO) 9 Co 3 Mo(CO) 2 (η-C 5 H 5 ) was solved by X-ray analysis.

A series of new coordination compounds is reported with dimethyl phthalate (MPH) as the ligand, viz. [M(MPH) 3 ](InCl 4 ) 2 with M=Mg(II), Ca(II), Mn(II), Fe(II), Co(II), Ni(II), and Zn(II). Each of the metal ions is bonded to three dimethyl phthalate molecules, the six carbonyl oxygens forming a regular octahedron. The carbonyl stretching vibration shifts to lower frequencies, the carbonyl bending vibration shifts to higher frequencies. The magnitudes of the shifts of these vibrations, the frequencies of the metal-ligand vibrations, and the melting points follow the Irving-Williams sequence.

Diazoketones 1, 8, 10 and 14 react with trialkyl phosphites to give different products depending upon the structure of the diazo compound, the type of the solvent and the nature of the phosphite ester used. Possible reaction mechanisms are discussed and the structural assignements are based on analytical, chemical and spectroscopic results.

The electronic structure and conformation in the gas phase of N-benzylideneaniline, its para-nitro and -methoxy as well as the ring perfluorinated derivatives were investigated by photoelectron (PE) spectroscopy and semiempirical molecular orbital (HMO) calculations. The π-ionizations were assigned and it is shown that these compounds in the gas phase are in a nonplanar conformation.

A comparison between calculated and observed values demonstrates that “ansätze” derived from an algebraic model in connection with appropriate boundary conditions are able to account for a quantitative description of the proton chemical shifts of allenes. Correlations of the proton chemical shifts with other NMR data, such as 13 C-chemical shifts and one-bond carbon-proton coupling constants, reveal some insigths into the nature of the 1 H substituent chemical shifts of alienes.

Decomposition of O-phenylcarbamoyl-salicylohydroxamic acid (8 a) in various systems yields benzoxazolin-2-one (4 a), salicylohydroxamic acid (10 a), aniline (9 a), and carbanilide (11 a), what is explained by two reaction paths via two different isocyanate intermediates.

The ozonation of maleic acid in aqueous solution (pH 3) leads to the formation of glyoxylic acid and formic acid which are oxidized to the stable endproducts oxalic acid and CO 2 in the further course of the reaction. With fumaric acid besides the double bond cleavage (75%) an anomalous ozonolysis is observed leading to the formation of the unstable intermediate mesoxalic acid semialdehyde which is oxidized to mesoxalic acid. In both cases 45% of the organic carbon appear as CO 2 after the complete elimination of the initial compounds. The specific ozone consumption in our experiments was 4 mmol O 3 per mmol of acid. On account of the quantitative follow up of the oxidation products the reaction mechanisms are discussed. The oxidation of glyoxylic acid, formic acid, oxalic acid and mesoxalic acid as pure substances by ozone gives qualitatively the same results as in the mixtures.

A product analysis was made for the reaction between some aromatic amines and 3-bromocamphor (2), which was invariably transformed into camphor (3) and eventually aryliminocamphor. The tertiary N,N-dimethylanilines were oxidized through a complex sequence of couplings and rearrangements to a number of diamines of the diphenylmethane type. Aniline (4) was also successful in the reductive debromination of 2 to 8 and camphor anil (7), but gave only tarry amino compounds. The reaction, carried out at 200 °C, appeared most probably to be triggered by the radicalic dissociation of the C-Br bond. Bromine ended up as bromide ion in a quantitative fashion.

The reaction of aryldiazo-4-tolylsulfones with benzene under the influence of aluminiumchloride has been investigated. Elimination of p-toluene-sulfinic acid is followed by evolution of nitrogen; substituted biphenyls can be isolated as main products. Aryl- and biphenylyl-4-tolyl-sulfoxides are formed by a consecutive process of the sulfinic acid as minor products. The arylation reaction presumably proceeds via the intermediate formation of aryl-diazonium ions.

The molecular orbital calculations for thieno(2,3-b)quinoline have been performed within the π-electron framework and by using the CNDO method. The calculated values for internuclear distances, atomic charges and reactivity indices for various types of reactions are presented and discussed.

The title compound crystallizes in the monoclinic space group P 2 1 /c with four molecules in the unit cell of dimensions a = 8.88(1), b= 20.86(3), c =14.14(2) Å, β= 111.27(5)°. The structure was determined by direct methods and refined to R = 0.046 (1777 independent reflexions). The eight-membered phosphorus-carbon-heterocycle has a boatconformation and the phenyl-substituent occupies the quasi-axial ring-position.

Anhydrous KBiO 3 was obtained for the first time; the synthesis was achieved by solid state reaction using high oxygen pressures. KBiO 3 is isostructural to KSbO 3 , a = 10.016(4) A.

The crystal structure of a phosphorusnitrogen compound with two-coordinate cationic phosphorus was determined from single crystal X-ray data. The structure of the molecule shows two very short P–N distances (161.4 pm) indicating 3p π (P)— 2pπ(N) interaction between the phosphorus and the lone pairs of the nitrogen atoms. The N–P–N angle was found to be 97.4°.

The crystal structure of R 2 N–P=NR (R = Si(CH 3 ) 3 ) was determined by single crystal X-ray data collected at —130 °C and refined to a conventional R-value of 0.029. The structure exhibits a two-connected phosphorus atom. The short P = N multiple bond (154.5 pm) indicates a 3p π (P)—2p π (Ν) interaction. The N–P–N angle was found to be 108.4°.

KSbSe 2 , prepared by heating a mixture of the elements in a silica tube, crystallizes triclinic with the following constants a = 1248.1(5) pm, α = 103.16(5)°, b = 644.5(5) pm, β = 99.27(5)°, c = 645.0(5) pm, γ = 99.44(5)°. There are SbSe 2 - -chains, formed by Ψ-tri-gonal bipyramids, which are connected by sharing edges.

The compounds A 3 Al 2 Si 2 (A = Ca, Sr, Ba) are isotypic to the analogous Ge-compounds and crystallize in an ordered variant of the Ta 3 B 4 -structure type.

After treatment of orthorhombic (BaSi 2 type of structure) bariumdigermanide at 40 kbar and 1000 °C in a belt type apparatus and quenching to ambient conditions a tetragonal polymorph (a-ThSi 2 type of structure) is obtained. Its crystal data are: I4 1 /amd, a = 0.4755 nm, c = 1.473 nm, z Ge = 0.415.

The quenchable high pressure phases of TlAlSe 2 and TlGaSe 2 are isotypic with TISe.

A compound Cu 3 TiO 4 was found to exist in the ternary system CuO-Cu 2 O-TiO 2 . The crystal structures of two modifications are very similar and contain Cu + with linear, Cu 2+ and Ti 4+ with trigonal distorted octahedral coordination.

The configuration of least electrostatic energy for the hydrogen atoms in both polytypes of MoO 2 Cl 2 · H 2 O was obtained by systematic variation of the orientations of the water molecules. The internal geometry of the H 2 O group was kept constant throughout the variation. The hydrogen bonds are of the bifurcated type: [xxx]

Kinetics of the piperidinolysis of active esters of acetic acid in acetonitrile and chlorobenzene was investigated. The rate data show intramolecular catalysis for the aminolysis of 2-nitro- and 2-cyanophenyl esters, while reactions of 2,6-disubstituted compounds are hindered by steric inhibition.