Band 62, Heft 9

Oxydation of (dpp-BIAN)Ca(THF) 4 with 0.5 equiv. of I 2 in THF yields [(dpp-BIAN)CaI(THF) 2 ] 2 (1). A corresponding neodymium compound [(dpp-BIAN)NdCl(THF) 2 ] 2 (2) has been obtained by reaction of (dpp-BIAN)Na 2 with NdCl 3 in THF. The X-ray single crystal structure analyses show 1 and 2 to be isostructural dimers containing octahedrally coordinated metal atoms bridged by the respective halides. The chelating dpp-BIAN ligand acts as a radical anion in the Ca 2+ complex 1 and as a dianion in the Nd 3+ complex 2, respectively.

Two complexes of silver(I) salts with ethylenediamine (etda) as a ligand were prepared and characterized. The study of the crystal structures (of the 2-hydroxy-4-nitro-benzoate trihydrate (1) and nitrate (2)) has shown that the formation of 2D and 3D coordination polymer networks results from etda ligands bridging the silver atoms which are connected via Ag-Ag argentophilic interactions.

Treatment of the μ 3 -oxo-centered mixed-valent trinuclear iron complex [Fe 3 (μ 3 -O)(μ-OAc) 6 - (H 2 O) 3 ] (1) in methanol solution with one, two, or three equivalents of 1-methyl-imidazole (C 4 H 6 N 2 ) afforded the substitution products [Fe 3 (μ 3 -O)(μ-OAc) 6 (H 2 O) 2 (C 4 H 6 N 2 )] (2), [Fe 3 (μ 3 -O)(μ-OAc) 6 - (H 2 O)(C 4 H 6 N 2 ) 2 ] (3), and [Fe 3 (μ 3 -O)(μ-OAc) 6 (C 4 H 6 N 2 ) 3 ] (4), respectively. Complexes 2 - 4 were characterized by spectroscopic and elemental analyses, and the crystal structures of complexes 3 · 1.5MeOH· 2H 2 O and 4 have been determined by single-crystal X-ray diffraction. The results indicate that in 2 - 4 the trinuclear core unit [Fe 3 (μ 3 -O)(μ-OAc) 6 ] of 1 is preserved.

The reactions of methyl(2-pyridyl)ketone oxime, (py)C(Me)NOH, with nickel(II) sulfate hexahydrate, in the absence of an external base, have been investigated. The reaction between equimolar quantities of NiSO 4 ·6 H 2 O and (py)C(Me)NOH in H 2 O leads to the mononuclear complex [Ni(SO 4 ){(py)C(Me)NOH}(H 2 O) 3 ] ·H 2 O (1 ·H 2 O), while an excess of the organic ligand affords the 1 : 2 compound [Ni(SO 4 ){(py)C(Me)NOH} 2 (H 2 O)] ·H 2 O (2 ·H 2 O). The structures of both compounds have been determined by single crystal X-ray diffraction. In both complexes the organic ligand chelates through its nitrogen atoms and the sulfate anion acts as a monodentate ligand. The thermal decomposition of complexes 1 ·H 2 O and 2 ·H 2 O has been studied. The IR data are discussed in terms of the nature of bonding and the structures of the two complexes.

The coordination chemistry of N-(2,6-di-methylphenyl)-2-hydroxy-3-methoxybenzaldimine (1) with Cu(II) has been investigated by X-ray crystallography, electronic and EPR spectroscopies, as well as by electro- and magnetochemistry. The title complex 2 crystallizes in the orthorhombic space group P2 1 2 1 2 1 (a = 8.1538, b = 17.7466, c =19.8507 Å). The mononuclear square-planar molecules 2 featuring trans-N 2 O 2 coordination are connected via weak intermolecular C-H· · ·π interactions into infinite chains parallel to the a axis. Although the intermolecular Cu· · ·Cu separations within individual chains and between chains are very long (8.154 and 9.726 Å ), the exchange interaction parameter G = 2.03 < 4, estimated from solid state EPR spectra, suggests the existence of long-distance superexchange pathways between adjacent Cu(II) centers. The electronic and electrochemical features of the compound are also discussed.

Reaction of Cd(CO 3 ) 2 , cinnamic acid and 2,2 ' -bipyridine (bpy) in CH 3 OH/H 2 O afforded a new chiral Cd(II) complex, Cd(bpy)(H 2 O)(PhCH=CHCO 2 ) 2 (1). Single crystal X-ray analysis shows that complex 1 crystallizes in the monoclinic space group P2 1 with the cell dimensions: a = 10.081(2), b = 9.2657(19), c = 13.748(3) Å , β = 103.02(3)°, V = 1251.2(4) Å3, Z = 2. The seven-coordinated Cd atoms are in a severely distorted capped trigonal prism geometry. The complex molecules are assembled via strong O-H· · ·O hydrogen bonds into chains along the [010] direction. Complex 1 exhibits weak fluorescence in the solid state at r. t.

Solid-state phase equilibria in the ternary systems Er-Ni-P and Er-Ni-As have been determined at 800 °C (region 0 - 67 at.% P or 0 - 50 at.% As) using X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Eight ternary phosphides and six ternary arsenides have been synthesized, including several phases reported previously. The hexagonal structure of the new compound Er 6 Ni 20 P 13 , as determined from single-crystal X-ray data, exhibits a new structure type closely related to the Ho 6 Ni 20 P 13 structure. Two other new phosphides, Er 16 Ni 36 P 22 (Tb 16 Ni 36 P 22 - type) and Er 20 Ni 42 P 30 (Sm 20 Ni 41.6 P 30 -type), have also been obtained at 800 °C. In the Er-Ni-As system, a new arsenide Er 20 Ni 42 As 30 (Sm 20 Ni 41.6 P 30 -type) has been found in addition to known ternary phases. From X-ray powder data, the structures of the ternary arsenides ErNi 4 As 2 (ZrFe 4 Si 2 -type) and Er 2 Ni 12 As 7 (Zr 2 Fe 12 P 7 -type) have been refined by Rietveld methods. In the single crystal investigations, two other new phases Er 12 Ni 30 P 21 [derived (La, Ce) 12 Rh 30 P 21 -type] and Er 13 Ni 25 As 19 (Tm 13 Ni 25 As 19 -type) have been prepared by high-temperature annealing (1500 °C).

Single crystals of ScPtP (orthorhombic, a = 6.437(1), b = 4.291(1), c = 7.550(2) Å ) were grown by reaction of the elements in molten lead (1000 °C), whereas LaPtP (orthorhombic, a = 7.268(1), b = 4.532(1), c = 7.864(2) Å ) was prepared by heating mixtures of the elements at 900 °C. Both phosphides were investigated by single crystal X-ray diffraction. Their crystal structures belong to the TiNiSi-type (Pnma; Z = 4), but the positions of the Ni and Si atoms are exchanged. Therefore the Pt atoms are located in the centers of trigonal prisms and the P atoms are coordinated by four Pt atoms in the shape of distorted tetrahedra.

Low-temperature X-ray structures and crystal packing arrangements are presented for di(4-iodobenzenesulfonyl)amine (4, monoclinic, P2 1 /c, Z ' = 1, isostructural to a previously described dimorph of the corresponding bromo homologue), 2,4-dimethylpyridinium di(4- iodobenzenesulfonyl)amide (5, monoclinic, P2 1 /n, Z ' = 1, isostructural to the corresponding bromo compound), and 3-methylpyridinium di(4-iodobenzenesulfonyl)amide (6, orthorhombic, Pna2 1 , Z '= 1). The packing of 4 consists of non-lamellar layers, in which the molecules are connected by N-H···O hydrogen bonds in one and by I δ+ ···O δ− interactions in the other dimension. Structure 5 involves strands of formula units, whereby the anions form catemers via I δ+ ···O δ− interactions and the cations are isotactically connected to the anion backbone by an N + - H(···O) 2 three-centre bond. Short I···I contacts are absent from structures 4 and 5. In contrast, structure 6 displays lamellar layers comprising an inner lamella of cations and N(SO 2 ) 2 groups connected by an N + - H···N − two-centre bond, and peripheral regions of 4-iodophenyl rings. Thus, the iodine atoms are efficiently shielded from the oxygen atoms, but in appropriate positions to form I δ+ ···I δ− interlayer contacts. Each structure is reinforced by a parallel-displaced π···π stacking arrangement of aromatic rings and an abundance of short C-H···A contacts (A = acceptor).

The structure of [Ph 3 PNPPh 3 ][(MeSO 2 ) 2 N] (monoclinic, P2 1 /c, Z ' = 1; single-crystal X-ray diffraction at −140 °C) displays chains of relatively small anions, surrounded by four parallel columns of bulky cations, giving a rectangular array. In contrast to a previously reported series of onium dimesylamides with smaller cations, interanion hydrogen bonding C Me -H· · · O, originating from the inductively activated methyl groups, is not observed in the present structure. In consequence, the packing arrangement is determined by multiple phenyl embraces between cations, weak cation-anion hydrogen bonds C Ph -H· · ·O/N and, most notably, by methyl-phenyl CH/π interactions between anions and cations. One methyl group forms two C-H· · ·π contacts to different phenyl rings (hydrogen-to-centroid distances: 272 and 285 pm), the other lies in a tripodal mode above an aromatic ring plane (hydrogen-to-centroid distances: ca. 330 pm).

In contrast with previous findings, triethylborane, BEt 3 , can act as a hydroborating reagent. Thus, the reactions of BEt 3 with alkyn-1-yl(trichloro)silanes, di(alkyn-1-yl)dichlorosilanes, alkyn- 1-yl(dichloro)vinylsilanes, trichloro(vinyl)silane, and dichloro(methyl)vinylsilane for several days in excess BEt 3 as the solvent at 100 - 120 °C were found to give exclusively products of 1,2- hydroboration. This unexpected behaviour was compared with that of tri-n-propylborane, BnPr 3 , and 9-borabicyclo[3.3.1]nonane, 9-BBN in analogous reactions, 9-BBN being a well established hydroborating reagent. All products were characterised by a consistent set of NMR data ( 1 H, 11 B, 13 C and 29 Si NMR).

One-pot microwave-assisted tandem deprotection of arylmethanesulfonates / nucleophilic aromatic substitution reaction (S N Ar) with activated aryl halides to synthesize asymmetrical diaryl ethers is described.

Malonyl-4,5-dihydroniphimycin was isolated as a new antibiotic from the mycelium of Streptomyces hygroscopicus 15. The chemical constitution was elucidated from the physico-chemical properties, using NMR techniques and mass spectrometry, to be a 36-membered macrolide related to non-polyenic antibiotics. Malonyl-4,5-dihydroniphimycin displays activity against filamentous fungi and Gram-positive bacteria.

A new bisdesmosidic furostanol saponin was isolated from leaves of Agave brittoniana Trel. Its structure was established as 3-[O-6-deoxy-α-L-mannopyranosyl-(1→4)-O-β -D-glucopyranosyl-( 1→3)-O]-[O-β -D-glucopyranosyl-(1→3)-β -D-glucopyranosyl-(1→2)-O-β -D-glucopyranosyl- (1→4)-β -D-galactopyranosyl)oxy]-(3β ,5α,6α,22α,2R)-26-(β -D-glucopyranosyloxy)-6,22-dihydroxy- furost-12-one. Its structural identification was performed using detailed analyses of 1 H and 13 C NMR spectra including 2D NMR spectroscopic techniques (DEPT, COSY, HETCOR and COLOC) and chemical conversions. The steroidal saponin showed no haemolytic effects in the in vitro assays and demonstrated antiinflammatory activity using in vivo models.

Corydalis taliensis Franch is a perennial herb used for treatment of rheumatic arthritis, toothache, and hepatitis. The chemical investigation of this plant resulted in the isolation of a new compound, named taliensineside (1). Its structure was identified on the basis of spectral evidence. In addition, thirteen known isoquinoline alkaloids (2 - 14) were isolated and identified by spectroscopic analysis and comparison of their spectral data with those reported previously.

Through our screening for new natural compounds, two 3,4,5-trisubstituted N-methyl-2-pyridone alkaloids, fusapyridons A (1) and B (2), along with the known compounds sambutoxin (3), Ndemethylsambutoxin (4), (-)-oxysporidinone (5), and the dimethyl ketal of oxysporidinone (6) were isolated from the fermentation extract of Fusarium sp. YG-45. Their structures were determined by spectroscopic analyses including NMR, MS, UV and IR. Compound 1 showed antimicrobial activity against Pseudomonas aeruginosa and Staphylococcus aureus.

Laportoside A (1), a new cerebroside, and a new ceramide named laportomide A (2), have been isolated from Laportea ovalifolia. Their structures were determined by comprehensive analyses of their 1D, 2D NMR, and HREIMS spectral data. The remaining two known compounds were identified as β -sitosterol acetate, and β -sitosterol glucopyranoside.

A novel phenylethanoid dimer, namely, jacraninoside A (1) and the five known constituents E/Z-acetoside (2), isoacetoside (3), cistanoside E (4), 6 '-acetylacetoside (5), and campneoside I (6) together with the seven flavonoids isoquercitrin (7), scutellarein 7-O-β -D-glucuronopyranoside methyl ester (8), apigenin 7-O-β -D-galacturonopyranoside (9), luteolin 7-O-β -D-glucuronopyranoside methyl ester (10), apigenin 7-O-β -D-glucuronopyranoside methyl ester (11), luteolin 7-O-β -Dglucopyranoside (12), and isovitexin (13) were isolated from the aqueous methanol extract of Jacaranda mimosaefolia D. Don. leaves. All known metabolites have been identified in this genus for the first time except for 2 and 12 which had been isolated once before from the leaves and twigs of Jacaranda mimosaefolia. Their structures were elucidated based on chemical evidences and spectroscopic analyses (1D and 2D NMR, HRMS ((-)-ESI)/MS, UV).

The crystal structure of 5-bis(thiomethyl)methylene Meldrum’s Acid (2) reveals a zwitterionic nature of the compound apparently influenced by both steric and electronic factors (triclinic space group P1̄, Z = 2, a = 5.489(1), b = 7.402(2), c = 14.329(3)Å ; α = 82.25(3), β = 82.08(3), γ = 78.59(3)°; V = 561.7(2) Å 3 ).

Single crystals of BiCl 3 ·CH 3 C 6 H 5 (1) formed from BiCl 3 and toluene have been analysed by X-ray crystallography (triclinic, P1̄, Z = 4, a = 7.308(2), b = 12.013(3), c = 12.284(2) Å , α = 75.02(2), β = 84.23(2), γ = 88.86(2)°, T = 173(2) K).