Volume 32, Issue 2

The new alkaline-earth oxocuprate(II) BaCuO 2 was prepared and investigated by single crystal X-ray methods. (Space group : O h 9 -Im 3 m, lattice constant: a = 1827 pm.) The distribution of 360 atoms per unit cell leads to a complicated polyhedral framework with Cu 2+ in well known square coordination. One of the Ba 2+ positions has the extraordinary coordination number 24.

Attempts to prepare BaCuO 2 single crystals with a flux of BaCl 2 and BaBr 2 respectively lead to new oxohalocuprates(II) : Ba 44 Cu 45 O 87 Cl 4 (A) and Ba 88 Cu 88 O 175 Br 2 (B). Single crystals were investigated by X-ray methods (cubic unit cell: (Α) a = 1827 pm, (B) a = 1830.3 pm, space group O h 9 -lm3m). The complicated crystal structures of both compounds are discussed. There are very interesting relationships to BaCuO 2 .

The crystal structure of Cs 2 [Pt(CN) 4 ] · H 2 O has been determined from X-ray diffraction data and refined to a conventional R value of 0.068 from 2210 reflections. The compound is hexagonal, α = 9.687(2) and c = 19.336(6) A, space group C 6 2 -P 6 1 , Z = 6. The given atomic coordinates represent the absolute configuration. The nearly square planar Pt(CN)4 2- groups form a helix with respect to the c axis. The distance between neighbouring Pt atoms in the helix is 3.543(1) A. The normal of the Pt(CN)4 2- group is tilted about 15 deg to the c axis leading to a considerable overlap of metal orbitals which is suggested from optical emission studies. The protons of the water molecules form hydrogen bonds to nitrogen atoms of different helices. Both Cs atoms have similar sevenfold coordination.

The title compound NiC 20 H 16 N 4 crystallizes in the monoclinic space group Ρ2 1 /a with unit cell dimensions a = 12.07(2) Å, b= 10.712(4) Å, c = 13.50(3) Å, β= 113.1(1)°. The structure was refined by a blockmatrix least squares procedure to R = 0.126, based on 1258 observed intensities. The planar molecules form centro-symmetric dimers in the solid state with interplane distances of 3.3 A.

The structure of N 3 P 2 SO 2 Cl 4 CH 3 was determined from three-dimensional X-ray data by direct sign determination. The heterocyclic compound with the endocyclic group N 3 P 2 S has a chair conformation.

Reduction of paramagnetic L 4 Co (L = (CH 3 ) 3 P) (d 9 ) by alkali metals affords salts of L 4 Co - (d 10 ). These are strong reducing agents, powerful bases and very able nucleophiles. They rapidly exchange three of their phosphine ligands for CO. Their reactions with a variety of inorganic and organic halides are shown to be effectively oxidative additions. From the distinct thermochromic behaviour of these salts both in the solid state and in solution a reversible formation involving different states of solvation is deduced.

Complexes of the type C 5 H 5 W(CO)(L)R (L = alkyne; R = CH 3 , C 6 H 5 ) are obtained by irradiation of a solution containing both C 5 H 5 W(CO) 3 R and L. The intramolecular mobility of the π-bonded acetylene in the 16-electron complexes C 5 H 5 W(CO)(L)R can be demonstrated by temperature-dependent 1 H NMR spectroscopy.

Chromyl chloride reacts with formic and acetic acids to give products which contain the trinuclear cation [Cr 3 O(OOCR) 6 (RCOOH) 3 ] + . The compounds have been characterized by elemental analyses, infrared spectral data, magnetic measurements and thermogravimetry.

A series of N-trimethylgermyl triorganophosphine imines have been prepared by three different routes, (1) from tertiary phosphines and trimethylgermyl azide, (2) from triorganophosphine imines and trimethylgermyl chloride and (3) by methylation of N-trichlorogermyl phosphine imines. With one exception all phosphine imines react with trimethylaluminium to yield 1/1-adducts. The new compounds were characterized by elemental analyses, molecular weight determinations, IR and 1 H and 31 P NMR spectra.

The three compounds N-2-(1,3-dimethyl-1,3,2-diazaboracyclopentyl)-N′,N′-dimethylhydrazine, (-CH 2 -NCH 3 -) 2 B-NH-N(CH 3 ) 2 ,N,N-bis-2-(1,3-dimethyl-1,3,2-diazaboracyclopentyl) -N′,N′-dimethylhydrazine, [(-CH 2 -NCH 3 -) 2 B] 2 N-N(CH 3 ) 2 , and N,N′-bis-2-(1,3-dimethyl-1,3,2-diazaboracyclopentyl)hydrazine, (-CH 2 -NCH 3 -) 2 B-NH-NH-B (-NCH 3 -CH 2 -) 2 , have been synthesized and characterized. The compounds can be viewed as mixed aminohydrazino-boranes; they exhibit relatively high chemical and thermal stability which appears to be due to the incorporation of the boron into the heterocyclic system.

(CF 3 ) 2 CNSCl (1) and amines, silylated amines, and silver salts react to form linear thiazenes and carbothiazenes e.g. [(CF 3 ) 2 C=N-S-] 3 N (5), (CF 3 ) 2 C=N-S-N = SF 2 (6), (CF 3 ) 2 C=N-S-N=S=N-SiR 3 (7), (CF 3 ) 2 C=N-S-NCO (8), and [xxx] (9).

The 29 Si chemical shifts of several trimethyl silyl derivatives of amines and amides are measured and compared to other chemical and theoretical properties such as the basicities or the electronic charge on the nitrogen or the hydrogen of the N-H group of the amine or the amide. Whereas the 29 Si chemical shift of saturated amines can be rationalized in terms of substituent effects, the shifts of aromatic amines show some dependency on the basic character of the amine. There seems to be little correlation between 29 Si chemical shifts and electronic charge, but there is a similarity of 29 Si with 1 H chemical shifts of the NH group, which is interpreted as depending on anisotropy effects.

The coordinatively unsaturated intermediates prepared by thermal decomposition of the phosphonium hydrogen cyanocobaltates were investigated by magnetic methods, IR and visible spectroscopy. Their reactions with amines and phosphines yield novel preparable species.

The compound (C 8 H 13 )PdClP(C 6 H 5 ) 3 has been synthesized and its structure determined from three-dimensional X-ray data.

ESCA data on the o-arylenedioxy chelates of silicon have been correlated with data on other organosilicon compounds using PAULING electronegativities. The data do not support p π → d π back bonding in the anionic chelates.

The new unsymmetrically 2,2′-disubstituted stilbenes with NO 2 , F, Cl, Br, OCH 3 , CH 3 and NH 2 groups as substituents have been prepared by WITTIG or PERKIN reactions. The compounds 1-8 were prepared due to the studies of fragmentation on electron impact, photochemistry and photoelectron spectroscopy. Their geometrical configuration has been established by 1 H NMR and IR spectra.

1,2,3-Trioxo-1,3,6,7-tetrahydro- 1H, 5H-benzo[ij]quinolizine (TMCHi) and 2,3-dihydro-1,2,3-trioxo-phenalene (PT) react with 2-aminopyridine to give the 2-pyridylimino-1,3-diones of type 1. However TMCHi and PT react under similar conditions with 3-aminopyridine to yield the corresponding ringclosed products of type 2. From TMCHi with two moles of 2-aminopyridine 2-oxo-1-(2-pyridylamino)-1,2,5,6-tetrahydro-4H-pyrrolo-[3,2,1-ij]quinoline (3) are formed.

The synthesis of specifically labelled (D, 18 O) cardenolides is described.

The method to generate the trichloromethylanion from chloroform and bariumhydroxide was used to prepare some substituted trichloromethyl-1,2-dihydropyridines and trichloroazabicyclo[4,1,0]heptenes.

A convenient and general route to the synthesis of 3,5-diaryl-2-(3H)-oxazolones has been developed. A number of hitherto unreported oxazolones have been prepared in almost quantitative yields. The structure of all these compounds have been characterised by IR, and elemental analysis and couple of them by NMR spectra. Attempt to extend this novel method to the synthesis of higher ring homologue, 1,3-oxazine, however, has not met with success.

Deaerated liquid acetaldehyde dimethyl acetal has been photolyzed at λ = 185 nm, and 28 products have been determined. The major ones with their quantum yields are: methanol (0.59), methane (0.26), ethyl methyl ether (0.17), methyl vinyl ether (0.16), methyl formate (0.14), ketene dimethyl acetal (0.1), ethane (0.06), hydrogen (0.06), and acetaldehyde (0.06). The major primary processes are suggested to be the scission of the C-OCH 3 bonds (homolytic and molecular) and of the O-CH 3 bonds (homolytic). Minor processes are hydrogen elimination reactions and the scission of the C-CH 3 bond.

Deoxygenated liquid pivalaldehyde dimethyl acetal was photolyzed at λ = 185 nm, and 28 products have been determined. The major ones and their quantum yields are: methyl formate (0.47), isobutene (0.39), methane (0.28), neopentane (0.16), isobutane (0.13), formaldehyde dimethyl acetal (0.13), formaldehyde (0.09), methyl neopentyl ether (0.09), methanol (0.07), and methyl pivalate (0.04). The predominant primary photoprocesses are suggested to be the scission of the O–CH 3 bond (homolytic, 0.51; molecular, 0.04) and the C-tBu bond (homolytic and molecular, 0.16). Minor processes are the scission of the C–OCH 3 (molecular, 0.09; homolytic, 0.03), C–H (0.006), and C–CH 3 bonds (< 0.01). The radical (A) eliminates with ease t-butyl (reaction (i)). This process is at least 10 times more efficient than methoxy elimination or hydrogen abstraction from the substrate. [xxx]

α-D-Glucose and β-D-fructose were γ-irratiated in the solid (polycrystalline) state at room temperature at doses of 3.5 · 10 20 -4.2 · 10 21 eV g -1 (dose rate 1.16 · 10 18 eV g -1 min -1 ). Carbohydrate products containing ≤ 6 carbon atoms were identified and their G-values (in parentheses) measured. Glucose: Dihydroxyacetone (1) (0.05), 3-deoxy-tetrose (2) (0.01 5 ), 1,4-dideoxy-2-pentulose (3) (0.05), 2,4-dideoxy-pentose (4) (0.08 5 ), 2,4-dideoxy-pentonic acid (5), 2,3-dideoxypentos-4-ulose (6) (together 0.03 5 ), threose (7), erythrulose (8), erythrose (9), erythronic acid (10) (together 0.04), 1-deoxy-2-pentulose (11) (0.005), 2-deoxy-ribose (12) (0.25), 3-deoxy-pentosulose (18) (0.02), 3,5-dideoxy-hexonic acid (14) (0.02), 2,3-dideoxy-hexonic acid (15) (0.01), arabinose (16) (0.25), ribose (17), ribonic acid (18) (together 0.02), 2-deoxy-2-C-hydroxymethyl-pentonic acid (19) (0.06), 5-deoxy-gluconic acid (20), 2deoxy-5-keto-glucose (21), 2-deoxy-gluconic acid (22), 2-deoxy-3-keto-glucose (28), 3-deoxy-glucosone (24), 3-deoxy-gluconic acid (25), 3-deoxy-4-keto-glucose (26), 3-deoxymannonic acid (27) (together 0.4). Identified but nor measured quantitatively were glucosone (28), 3-keto-glucose (29), 4-keto-glucose (30), 5-keto-glucose (31) and gluconic acid (82). G(H 2 ) = 5.75; G(CO 2 ) = 0.7. Fructose: 7-9 (together 0.65), 3-deoxy-pentonic acids (37), 3-deoxy-pentosulose (88) (together 0.3), arabonic acid (89) (0.1), 18 (0.05), 6-deoxy-2,5-hexodiulose (40) (40). Identified but not measured quantitatively were glyceraldehyde (34), butanone-(3)-diol-(1,2) (35) and 2- and 3-deoxy-hexodiuloses. G(H 2 ) = 4.75, G(CO 2 ) = 0.05. Reaction schemes are proposed to account for the formation of the products. The scission of the hemiacetal bond and of the C-Η and C-C bonds next to it appears to be typical for solid state irradiations. The formation of deoxy-compounds is observed both in the solid state and in aqueous solution. The formation of dideoxy-compounds is only prominent in the solid state. In polycrystalline fructose a chain reaction is induced leading to 6-deoxy-2,5-hexodiulose (40).

2-Furan carboxaldoxime (anti-form) or anti-furan 2-aldoxime (FDH) forms octahedral complexes of the type M(FDH) 2 Cl 2 (M = Mn, Co, Ni, Cu and Zn) and M(FDH) 3 Cl 3 (M = Cr and Fe). The infra red spectral studies have revealed that the coordination of the metal involved the oxime oxygen and the furan ring oxygen. However, the ligand acts as bidentate in case of M(FDH) 2 Cl 2 while it is monodentate in M(FDH) 3 Cl 3 . The M-O bands in the infrared spectra may be taken as a criterion for the denticity of the ligand in its various metal complexes. Bands at 670-630 cm -1 and around 450 cm- 1 indicate the bidentate ligand, while the absence of the band at 670-630 cm- 1 reveals monodenticity. The : C=N-stretching frequency has been found to increase with decreasing stability of the bivalent metal complexes, while it is insensitive in case of the trivalent metal complexes.

CH 3 P(S)(NCO) 2 reacts with [(CH 3 ) 3 Si] 2 N-CH 3 , [(CH 3 ) 3 SiNCH 3 ] 2 CO and [(CH3) 3 Sn] 3 N to give the cyclic compounds 2a-2c. The structures are discussed on the basis of NMR and IR data. In 2 a and 2 b the (CH 3 ) 3 Si-groups are easily and quantitatively replaced by protons with water under formation of (CH 3 ) 3 Si-O-Si(CH 3 ) 3 . By the reaction of CH 3 P(S)(NCO) 2 with [(CH 3 ) 3 Si] 2 S 4 is obtained, a cyclic compound with a sulfur atom of coordination number 2. FP(S)(NCS)2 was used to investigate the scope of these reactions. With [(CH 3 ) 3 Si] 2 NCH 3 and FP(S)(NCS)2 5 is obtained, which reacts with S 2 Cl 2 to yield 6, a bridged disulfur compound. This method may be useful for the systematic investigation of new cyclic compounds.

The sulfinato-O complex (p-CH 3 C 6 H 4 S(O)O) 2 Pd(en) (2a) and its ionization isomer, the ionic compound [Pd(en) 2 ][p-CH 3 C 6 H 4 SO 2 ] 2 (2b), are obtained from 1 by ligand addition in dependence of the nature of the solvent. 2 a, b can be transformed into each other reversibly. For 2 a two structural models are discussed. The pseudooctahedral configuration with two bidentate ethylene diamine and two sulfinato-O ligands in trans position seems to be more likely.

The reactions of the halogenocyclotriphosphazatrienes N 3 P 3 Fe 6 and N 3 P 3 Cl 6 with the reagentsMe 3 SiR [R = NP(NMe 2 )3, NPMe 3 , NPMe 2 Ph, NPMePh 2 , NPPh 3 , and NP(OEt) 3 ] are discussed, and conclusions are drawn about some of the factors controlling the course and rate of these reactions. Some novel phosphazenyl-derivatives, N 3 P 3 X 5 R [X = F or Cl, R = NP(NMe 2 ) 3 ; X = F, R = NP(OEt) 3 ] are reported.

Pentacarbonyl(methoxyphenylcarbene)-chromium(0) and ß-diketonesR 1 COCH 2 COR 2 (R 1 , R 2 = CH 3 , CF 3 , NHCONH) react on heating to give the meso-, RR- and SS-configurational isomers of 1,2-dimethoxy-1,2-diphenylethane.

The exchange of a protons for deuterium or tritium in di-N-nitrosohomopiperazine and in di-N-nitroso-2,6-dimethylpiperazine is described. It is shown that an exchange in bifunctional N-nitrosamines occurs in all acidic positions, even in those which are sterically hindered. In addition, it is demonstrated that a protons will also exchange for tritium in 3 H 2 O enriched H 2 O, using KOH.