Band 37, Heft 8

The crystal structure of the title compound has been determined (P3c 1, a = 2161.5(3), c = 2859.8(4) pm, Z = 6; R w = 0.07 for 2217 observed reflections). There are three independent (Ph 3 Sb) 4 Au + cations, each with one Au-Sb bond directed along a crystallo-graphic threefold axis. Deviations from ideal tetrahedral coordination are small (max. 8 pm, 1°).

Au(SeO 3 )Cl was prepared in a sealed-tube synthesis from Au 2 Se 4 O 11 , selenic acid and perchloric acid. The crystal structure was determined (P1̄, a = 418.5(1), b = 975.6(4), c = 1060.8(5) pm, α = 80.57(2), β = 88.85(2), γ = 87.66(2)°, Z = 4, R = 0.06 for 2273 observed reflections). There are three independent gold atoms in the structure, belonging to AuO 4 , AuO 2 Cl 2 and AuO 3 Cl units respectively. The oxygen atoms bridge Au and Se, leading to a polymeric layer structure.

The Compound [S(AUPPh 3 ) 2 ] · CH 2 Cl 2 was prepared from Ph 3 PAuCl and H 2 S in CH 2 Cl 2 and characterised by X-ray structure determination [P2 1 /c, a = 1851.6(4), b = 2225.1(6), c = 880.3(2) pm, β = 96.32(1)°, Z = 4, R = 0.053]. A constrained refinement of the light atom positions was necessary because of pseudosymmetry. Ph 3 PAuPF 6 reacts with Se(Sn)(CH 3 ) 3 ) 2 to give [Se(AuPPh 3 ) 3 ] + PF 6 - which was also characterised by X-ray methods [P1̄, a = 1539.5(6), b = 1800.5(7), c = 2289.5(9) pm, α = 89.35(3), β = 72.44(3), γ = 69.75(3)°, Z = 4, R = 0.061]. There are two formula units in the asymmetric unit. Both structures show short Au···Au contacts (ca. 300-340 pm).

Coordination properties of phosphorus ylides towards electropositive metals are greatly improved in systems, where the carbanionic charge can be delocalized into the aromatic rings of substituents, as illustrated in the title compounds. The ferrocenyl-substituted ylide 2, synthesized from bis(diphenylphosphino)methane and (ferrocenyl)trimethyl-ammonium iodide via the phosphonium salt intermediate 1, is thus easily converted into the alkali complexes 3 a, b on treatment with NaNH 2 or KH in tetrahydrofuran, respectively. The intensely coloured products are soluble in a number of organic solvents. NMR spectra of these solutions provide evidence for an interaction between alkali cations and the ferrocenyl rings. - From (C 6 H 5 ) 2 CH 2 P(C 6 H 5 ) 2 and ferrocenylmethyl chloride a di-quaternary salt 4 is obtained, which yields a double-ylide mixture 5 a, b on treatment with base. Hydrolysis of this product affords the ylidic phosphine oxide 6. - The reaction of the ylides 7 and 9 (described previously) with NaNH 2 , KH or barium metal (in liquid ammonia) leads to the (earth) alkali complexes 8a-c and 10a, b, respectively. With the exception of 8c, but similar to 3a, these materials contain tetrahydrofuran solvate molecules. The 23 Na NMR spectrum of 8a and the pronounced quadrupole broadening of the P(III) signals by the alkali cations in the 31 P NMR spectra of 8 a, b allow structural suggestions for the solution state as proposed in the formulae. Further treatment of 10b with KH yields a potassium complex 11, characterized, i.a., via a corresponding diquaternary salt 12.

The compounds Li[ n C 4 H 9 VO(O t C 4 H 9 ) 3 ], Me 3 SiCH 2 V(O t C 4 H 9 ) 3 , (CH 3 ) 2 V(OSiMe 3 ) 2 and V(O t C 4 H 9 ) 4 have been prepared by reaction of esters VO(OR) 3 (R = t C 4 H 9 , SiMe 3 ) with lithium alkyls. RVO(O t C 4 H 9 ) 2 species are not formed by direct alkylation of VO(O t C 4 H 9 ) 3 with LiR; albeit in small yields, these compounds (R = CH 3 , CH 2 SiMe 3 ) can be synthesized however from VO(O t C 4 H 9 ) 2 Cl. The 51 V, 1 H and 13 C NMR spectra of the vanadium(V) and vanadium(IV) compounds are discussed; the constants of 51 V, 1 H and 51 V, 13 C coupling have been determined.

Carbonic ester phosphides, RPHCOORʹ and RP(COORʹ) 2 , have been prepared by the reaction of ClCOORʹ with primary phosphines RPH 2 in the presence of K 2 CO 3 . Some compounds of RPHCOORʹ series are transformed into P-heterocycles through addition of the P-H group to the C = C doublebond systems. The 31 P NMR data, IR and mass spectra of the novel compounds are presented and discussed.

The new compound Ca 3 AlAs 3 crystallizes in the orthorhombic system (space group: Pnma) with a = 1221.2(3) pm, b = 420.1(2) pm, c = 1343.4(4) pm. In the structure there are AlAs 4 -tetrahedra connected by common corners to „Einereinfach" chains. The new compound Ba 3 AlSb 3 crystallizes in the orthorhombic system (space group: Cmca) with a = 2113.3(10) pm, b = 719.4(5) pm, c = 1400.9(8) pm. AlSb 4 -tetrahedra are connected by common edges to isolated Al 2 Sb 6 groups. According to the compositions and structures both compounds belong to the Zintl-phases.

Hitherto unknown LiSrFeF 6 was obtained by heating mixtures of binary fluorides [LiF + SrF 2 + FeF 3 ; Li:Sr:Fe = 1:1:1] under argon [Au tubes, 500 °C, 2 d or 650 °C, 14d] as a colourless powder or colourless single crystals. LiSrFeF 6 crystallizes monoclinicly in P2 1 /c-C 5 2 h with a = 5,2972(4), b = 8,7989(8), c = 10,2257(7) Å, β = 92,212(8)°, Z = 4; d rö = 3,69 und d pyk = 3,66 g · cm -3 , positions are given in the text, R = 9,1 6 % (R w = 6,8 3 %) for hkl (Mo-K a , 4-circle diffractometer data).

By pressure fluorination in monel autoklaves samples of LiCuCoF 6 (rutile type structure), LiMgCoF 6 , LiNiCoF 6 and LiZnCoF 6 (trirutile type structure), LiCdCoF 6 , LiCaCoF 6 , LiCaNiF 6 and LiSrNiF 6 (LiCaAlF 6 -type [2] structure), LiSrCoF 6 (LiSrFeF 6 -type structure [3]) and LiBaCoF 6 (LiBaCrF 6 -type structure [4]) were synthesised for the first time. The Madelung Part of Lattice Energie, MAPLE, is studied and discussed. By magnetic measurements we obtained new information on the structure of fluorotrirutile.

Tetrabromo- and -iodothallates(III) of the alkali cations crystallise from aqueous solutions as cubic hydrates MTlX 4 ·nH 2 O (M = Li, Na, K, Rb, Cs, NH 4 ; X = Br, I; n = 1-2). The tetraiodothallates retain their cubic structure on dehydratisation, while the tetrabromothallates undergo structural changes. The X-ray structure analyses of RbTlBr 4 · H 2 O, NH 4 TlBr 4 · 2H 2 O and KTlBr 4 · 2H 2 O (-50 °C) showed that these compounds consist of a three-dimensional framework of TlBr 4 tetrahedra and MBr 12 ikosahedra which reminds of zeolites. In cavities of this framework 2/3 of the alkali cations and the crystal water molecules are accommodated in a disordered manner.

The molecular structures of the title compounds have been determined by X-ray methods. In the bis(trimethylsilyl) substituted dithietane the (CH 3 ) 3 Si groups are in trans position; the C 2 S 2 -ring is planar. In the cyclobutanone the pyrrolidine group occupies an equatorial position, as does the phenyl group in the cyclobutanol. In the latter the hydroxyl group is trans to the pyrrolidine ring. The four-membered carbon rings are folded.

The crystal and molecular structures of (PPh 4 ) 2 [(WS 4 )WS(WS 4 )] (1a) and CS 2 [(WS 4 )WO(WS 4 )H 2 O] · 2 H 2 O (2a), which contain the first reported isopoly-thioanion of a transition metal have been determined: 1a: (P1̅, a = 913.0(1), b = 1060.1(2), c = 1333.9(2) pm, α = 87.11(1), β = 85.18(1), γ = 83.07(1)°, V = 1277.6 · 10 6 pm 3 , Z = 1); 2a: (P2 1 /n, a = 671.6(2), b = 2018.5(4), c = 714.4(2) pm, β = 101.42(2)°, V = 949,3 · 10 6 pm 3 , Z = 2) and compared with that of the trimetallic heteropoly-thioanion of (AsPh 4 ) 2 [(WS 4 )Ni(WS 4 )] (3a). 3a: (P1̄, a = 1255.2(3), b = 1277.1(3), c = 939.0(2) pm, α = 113.19(2), β = 96.28(2), γ = 108.72(2)°, V = 1261.5 · 10 6 pm 3 , Z = 1). Though there are delocalized orbitals in the isopoly-thioanions they can be regarded as coordination compounds of W IV X 2+ containing two W VI S 4 2- ligands.

Several bis(oxalato)borates and bis(malonato)borates have been prepared in heterogeneous reaction from boric acid, dicarboxylic acid and dicarboxylic salt by refluxing in benzene under continuous separation of water. The compounds were characterized by their IR and 11 B NMR spectra. The vibrational spectra of the bis(oxalato)borate are discussed in detail.

The syntheses and reactions of sulfur coordinated ruthenium centers with CO, PR 3 , (R = Me, Ø), N 2 H 4 and N 2 are investigated. Reaction of [Ru(CO) 3 (THF)Cl 2 ] with lithium-o-methylthiobenzenethiolate yields cis-[Ru(CO) 2 (CH 3 S-C 6 H 4 -S) 2 ], with Li 2 -o-benzenedithiolate the cis-[Ru(CO) 2 (C 6 H 4 S 2 ) 2 ] 2- -ion is obtained, which can be isolated either as the NMe 4 salt or reacted further with 1,2-C 2 H 4 Br 2 to give cis-[Ru(CO) 2 dttd], (dttd 2- = 2,3,8,9-Dibenzo-1,4,7,10-tetrathiadecane 2- ). In all three complexes the CO ligands are relatively inert to substitution; refluxing of [Ru(CO) 2 (C 6 H 4 S 2 ) 2 ] 2- in EtOH in the presence of excess PMe 3 , however, and subsequent alkylation with 1,2-C 2 H 4 Br 2 yields [Ru(CO)PMe 3 (dttd)]. [Ru(PMe 3 ) 2 dttd] is obtained from [Ru(PMe 3 ) 4 Cl 2 ] and Li 2 -dttd, the synthesis of which is also described. In [Ru(PMe 3 ) 2 (dttd)] the PMe 3 ligands are inert, but in [Ru(PØ 3 ) 2 (dttd)] one PØ 3 ligand is easily substituted by CO or N 2 H 4 yielding [Ru(CO)(PØ 3 )dttd] or [Ru(N 2 H 4 )(PØ 3 )dttd] respectively; [Ru(PØ 3 ) 2 (dttd)] is obtained from [RU(PØ 3 ) 3 Cl 2 ] and H 2 -dttd. The complexes are characterized by elemental analyses, IR, 1 H NMR and mass spectroscopy.

The infrared spectra (200-4000 cm -1 ) of trans- and cis-Pt(NX 2 CH 2 COO) 2 (X = H, D), trans- and cis-PtCl 2 (NH 2 CH 2 COOH) 2 , trans-PtCl 2 (NH 2 CH 2 CO 2 Et) 2 , cis-PtCl 2 (NX 2 CH 2 CO 2 Et) 2 , cis-PtCl 2 (NX 2 CH 2 NXCH 2 CO 2 Et) 2 (X = H, D) and cis-PtY 2 (NH 2 CH 2 NHCH 2 CO 2 Et) 2 (Y = Br, I) including 15 N derivatives have been studied. There is no appreciable change of vibrational frequencies for corresponding cis- and trans- complexes which could be attributed to the trans-influence of different ligands. Due to lower symmetry most of the absorptions of the cis-complexes are split into doublets compared with the trans-compounds.

The reaction of Pt(COD) 2 with cis-[RPNCR 3 ] 2 (1), R = CH 3 , affords the two-coordinate platinum(0) complex PtL 2 (2) (L = diazadiphosphetidine 1). In benzene solution PtL 2 , Pt 2 L 3 (3) and L are in equilibrium. 2 and diphenylacetylene or fumaric acid dinitrile give the platinum diazadiphosphetidine complexes L 2 Pt(PhCCPh) (4) and L 2 Pt[H(NC)CC(CN)H] (5), L = 1.

Metal complexes of the type M(CO) 5 L (M = Cr, W), MX 2 L 2 (M = Pd, Pt; X = Cl, Br, I), PtCl 2 (L)PPh 3 , and [Pt(Cl)(L)(PPh 3 ) 2 ]BF 4 have been prepared with L = CNCH 2 SO 2 C 6 H 4 -pCH 3 , CNCH 2 Ph, and CNCHPh 2 , and reacted with a variety of nucleophiles (NH 2 CH 2 CO 2 CH 3 , CH(CN) 2 -, CH(CN)CO 2 CH 3 -, OH-) and 1,3-dipolarophiles (CF 3 CN, CH 3 O 2 CC ≡CCO 2 CH 3 , CH 2 = CHCN, RNCO (R = CH 3 , Ph), RCHO (R = i-C 3 H 7 , Ph, C 6 H 4 -oOH)) to give carbene, α-aminovinyl, and carboxamido complexes, and C2-metallated heterocycles (imidazoles, pyrroles, oxazolos, oxazolines), respectively. Ready dealkylation occurs of benzhydryl isoeyanide in [Pt(Cl)(CNCHPh 2 )(PPh 3 ) 2 ]BF 4.

The 1 H and 13 C NMR spectra of various alkylsubstituted η 3 -allyl-η 5 -cyclopentadienyl-nickel complexes were analysed with the help of two dimensional correlation ( 1 H- 1 H and 1 H- 13 C) NMR. The use of two dimensional NMR techniques for the routine analysis of complicated NMR spectra is demonstrated.

The photochemical reaction of decacarbonyl-dirhenium(0) (1) with 1,3-butadiene yields a mixture of six complexes, which were isolated by HPL-chromatography and characterized by spectroscopic means. As minor products the allylic complexes E and Z tetracarbonyl-η 3 -1-buten-3-yl-rhenium(I) (2, 3) and RR, SS and SR ≡ RS Octaearbonyl-μ-[1-3:6-8-η-(1,6-octadiene-3,8-diyl)]-dirhenium(I) (7, 8) are obtained. Reaction temperatures of 240 K favour the formation of the novel μ-hydrido-octacarbonyl-μ-[1-2-η-1-δ-(1,3-butadien-1-yl)]-dirhenium(I) (4). At lower temperatures (188 K) octacarbonyl-η-s-cis-1,3-butadienedirhenium(0) (5) results in comparable amounts. 4 rearranges in solution to octacarbonyl-μ-η-trans-1,3-butadiene-dirhenium(0) (6).

[Ni(3ʹ,5ʹ-cGMP)(H 2 O) 5 ][3ʹ,5ʹ-cGMP] · 5H 2 O (1) was isolated from an aqueous solution of Ni(NO 3 ) 2 and guanosine 3ʹ,5ʹ-cyclic monophosphate at a pH of 6.5. 1 is orthorhombic P2 1 2 1 2 1 with a = 19.020(4), 6 = 7.718(1), c = 12.316(2) Å, Z = 2, D c = 1.70 g·cm -3 . The structure was refined to R = 0.085 and R w = 0.077 for 1364 independent reflections. The structure of 1 is disordered. The nickel atom has a site occupation factor of 0.5 with the 3ʹ,5ʹ-cGMP moieties of both cation and anion disordered over the same fourfold general positions. Direct metal binding of the purine N(7) is observed with the octahedral co-ordination of the nickel atom being completed by 5 water oxygens, one of which forms an intramolecular O-H···O hydrogen bond to the guanine O(6). The purine base adopts the syn conformation relative to the ribose ring with x CN = -93.3(8)°. The nucleotide bases are stacked in columns along the b screw dyad axes. Parallel to these columns are cavities which are filled by the water molecules and the complexed nickel cations.

Seven new analogs of the luteinizing hormone releasing hormone (LHRH), having an Azagly 10 moiety, and three corresponding Gly 10 -analogs were synthesized for bioassay and comparison of inhibitory potencies. This study was toward a possible advantage of the Azagly 10 moiety to minimize C-terminal degradation, in vivo. Of the three procedures which were studied to achieve Azagly 10 -peptides, the reaction of cyanate ion with hydrazides was the most favorable. Variations of substitution in position 1 were also studied. The data from the antiovulatory assay showed that an Azagly 10 moiety may not depress activity, and may allow equal or even higher activity than the Gly 10 moiety, depending on the analog. [N-Ac-D-Thr 1 , D-p-Cl-Phe 2 , D-Trp 3,6 , Azagly 10 ]-LHRH was more inhibitory than the corresponding Gly 10 -analog. Based on pairs of analogs, the following relationships appeared: (1) N-Ac-D-Thr 1 was more effective than N-Ac-p-Cl-Phe 1 ; (2) The L-configuration of Ala as N-Ac-Ala 1 - was more effective than the D-; (3) N-Ac-Ala 1 appeared more effective than the N-Ac-D-Thr 1 ; (4) D-Trp 6 appeared more effective than D-Phe 6 . In an ultimate clinical use of an antagonist of LHRH to block ovulation, the Azagly 10 moiety may be advantageous for limitation of enzymatic degradation.

The syntheses of the platinum-organic compounds cis-[Pt(PPh 3 ) 2 (X-C 6 H 4 )Cl] (X = H, 3-H 3 C-, 3-H 3 CO-, 4-H 3 C-, 4-H 3 CO-) and cis-[Pt(PPh 3 ) 2 (X-C 6 H 4 )Br] (X = H, 3-H 3 C-, 3-H 3 CO-, 3-(H 3 C) 2 N-, 4-H 3 C-, 4-H 3 CO-) are described; their thermal isomerization in crystalline phase are studied and the resulting trans-isomers characterized.

3,5-Dihydroxy-4-formyl-7-methoxy-6-methyl-1(3H)-isobenzofuranone [=cyclopaldic acid] (1) and 5-hydroxy-4-hydroxymethyl-3,7-dimethoxy-6-methyl-1(3H)-isobenzofura-none [= 3-O-methyl cyclopolic acid] (2) were isolated from Aspergillus duricaulis-, those compounds were found to be antibiotically active.

An X-ray structure determination of TaCl 5 · S 4 N 4 shows that the S 4 N 4 group is bonded via one of its nitrogen atoms to the Ta atom thus completing the coordination octahedron around the tantalum center.