Volume 51, Issue 7

Single crystals of Ba 2 Mn(B 3 O 6 ) 2 (I) and Ba 2 Co(B 3 O6) 2 (II) were prepared by using a B 2 O 3 flux technique, Ba 2 Mn(B 3 O 6 ) 2 in an argon atmosphere. X-ray investigations on single crystals of both compounds yield the space group C 3i 2 R3̄ (No. 148) with 3 formula units in the cell of dimensions (I) a = 711.01(4), c = 1694.90(3) pm and (II) a = 707.2(2), c = 1673.8(1) pm. The crystal structure is built by nearly planar (B 3 O 6 ) 3- rings and contains one ninefold coordinated Barium site. Mn(I) and Co(II) are octahedrally coordinated by oxygen. The compounds are isotypic to B 2 Ca(B 3 O 6 ) 2 .

The compounds MnCo(B 2 O 5 ) (I) and MnMg(B 2 O 5 ) (II) were prepared by using B 2 O 3 flux techniques in an argon atmosphere. X-ray investigations on single crystals showed triclinic symmetry, space group C i 1 - P1̄, I: a = 320.94(10), b = 619.20(11), c = 939.0(2) pm, a = 104.38(2)°, β = 90.76(2)°, γ = 92.046(14)° and II: a = 318.97(7), b = 619.8(2), c = 936.7(2) pm, α = 104.47(2)°, β = 90.60(2)°, γ = 91.98(2)° Z = 2. Their structures are isotypic with Co 2 (B 2 O 5 ). All metal ions are octahedrally coordinated by six oxygen atoms. The structures contain diborate anions B 2 O 5 4- . Each boron atom is threefold coordinated by oxygen.

A new modification of Na 2 Zn 2 O 3 has been synthesized via solid state reaction. According to the single crystal structure determination, the compound crystallizes in the space group P4 3 2 1 2 (No. 96) with lattice parameters a = 6.1812(2), c = 9.4479(4) Å, Z = 4. The structure consists of ZnO 4 tetrahedra connected via edges and corners forming a threedimensional network. The structure can be described as an distorted anti spinel.

The synthesis of N(CH 2 PPh 2 ) 3 (1) and its spectroscopic properties are reported. Reaction of N(CH 2 PPh 2 ) 3 with (CH 3 CN) 3 Mo(CO) 3 leads to N(CH 2 PPh 2 ) 3 Mo(CO) 3 (2). The cationic complex [HN(CH 2 PPh 2 ) 3 Mo(CO) 3 ] + (3) is obtained by protonating the N atom of 2 with aqueous HBF 4 . The spectroscopic and structural properties of 2 and the cation 3 are compared. The results indicate an interaction of the ligand N atom and the Mo atom through space over more than 350 pm. It is shown from IR data that 2 is fixed on silicagel by hydrogen bonding.

Dark green single crystals of Sr 2 (VO)P 2 O 8 have been prepared by solid state reactions in closed quartz tubes. X-ray investigations led to monoclinic symmetry, space group C 2h 6 -I2/a, a = 6.744(4), b = 15.866(4), c = 7.032(2) Å, β = 115.41(2), Z = 4. Sr 2 (VO)P 2 O 8 is isotypic to Sr 2 (VO)V 2 O 8 and shows V 4+ in split positions. The split positions are in non-centric octahedral coordination forming a short vanadium to oxygen distance typical for the vanadyl group. The crystal chemistry of the monovanadyl orthophate Sr 2 (VO)P 2 O 8 is discussed considering related divanadyl phosphates.

Phosphinoalkylnitriles R 2 P-(CH 2 ) n -CN {R = isopropyl ( i pr), phenyl (ph), cyclohexyl ( c hex), n = 3, 6, 10} have been prepared starting from the corresponding secondary phosphines in an easy three step synthesis. All new compounds were characterized by their 1 H -, 13 C and 31 P NMR data. Some of these new P, N ligands were used to prepare complexes [{R 2 P- (CH 2 ) n -CN} 2 PdCl 2 ] which were also identified by their NMR data. In addition the crystal structures of three derivatives, [{ i pr 2 P-(CH 2 ) 3 -CN} 2 PdCl 2 ] 7a, [{ph 2 P-(CH 2 ) 3 -CN} 2 PdCl 2 ) 7b and [{ph 2 P-(CH 2 ) 6 -CN} 2 PdCl 2 ] 8b were determined by X-ray analysis. The coordination mode of the phosphinoalkylnitriles in these complexes was found to be P-bonded resulting in a trans configuration. Palladium catalysts with 5a as ligand show high activies in the co-oligomerization of butadiene and carbon dioxide. The δ-lactone 11a is formed under very mild conditions.

Single crystals of [Cd(pyrazine)Cl 2 ],[Zn(pyrazine)Cl 2 ] and [Zn(pyrimidine)Cl 2 ] were obtained by a diffusion technique from aqueous solutions of the metal dichlorides and solutions of the respective diazine. The structures consist of “supramolecular” networks of-M-Cl-M - and -M-diazine-M-chains.

From the binary systems M 2 SO 4 /H 2 SO 4 (M = Ba. Sr), two new hydrogen sulfates, (Ba(HSO 4 ) 2 (H 2 SO 4 ) 3 and Sr(HSO 4 ) 2 (H 2 SO 4 ), have been synthesized and structurally characterized. Ba(HSO 4 ) 2 (H 2 SO 4 ) 3 crystallizes in the orthorhombic space group P2 1 2 1 2, with unit cell parameters a = 4.680(1), b = 11.267(2), c = 29.188(6)A, Z = 4. BaO 9 trigonal prismatic polyhedra with Ba-O distances of 2.68 - 3.02 Å from nine different SO 4 tetrahedra are connected via common bases and build “isolated” columns consisting of O-S-O bridged double chains along the x-axis. HSO 4 and H 2 SO 4 tetrahedra are linked via hydrogen bonds to form columns. Sr(HSO 4 ) 2 (HTSO 4 ) crystallizes in the triclinic space group P1̄ with unit cell parameters a = 5.971(1), b = 8.468(2), c = 10.226(2)Å, α = 81.71(3), β = 83.30(3), γ = 70.69(3)°, Z = 2. Sr is coordinated by nine oxygen atoms from seven different SO 4 tetrahedra with Sr-O distances of 2.47 - 2.84 Å. The SrO 9 polyhedra build layers consisting of O-S-O bridged chains. Three crystallographically different SO 4 tetrahedra are linked via hydrogen bonds to form a kind of flattened cylinder along the x-axis.

The photolytically induced CO-substitution reaction of CpMn(CO) 3 with N-benzyl-aziridine leads to the first mono coordinate aziridine complex, . It is stable against thermal C 2 H 4 elimination up to 135°C. No nitrene complexes {Cp(CO) 2 Mn} n NBz (n = 1, 2) were detected. The X-ray structure analysis of shows the intact three-membered ring ligand and the pyramidal configuration of the nitrogen atom.

The lanthanum(III) and dysprosium(III) complexes of triethylenetetramine-N, N, N′, N″, N‴, N‴-hexaacetic acid (H 6 ttha) were prepared and isolated as guanidinium salts:[C(NH 2 ) 3 ] 2 [La(Httha)] · 3 H 2 O and [C(NH 2 ) 3 ] 2 [Dy(Httha)] · 5 H 2 O. The X-ray crystal structure of both complexes was determined: In the La(III) complex (space group P1̄) all donor atoms (N 4 O 6 ) are coordinated. The coordination number 10 is realized in a bicapped square antiprism (SAPRS-10). The bond length La to O of the protonated carboxylic group is ca. 0.3 Å longer than the other five La-O distances. The Dy(III) complex (space group P1̄) exhibits coordination number 9 in a monocapped square antiprism (SAPRS-9). The protonated carboxylic group is not coordinated.

The title compound. α-Na 7 [H 3 SiW 9 O 34 ]-9H 2 O. is the first a-isomer of heteropolyoxometalate anions [XW 9 O 34 ] 2- . Its crystal structure is interesting because of the unusual coordination chemistry of the Na + cations and the formation of a microporous solid. While one of the three crystallographically independent Na + cations is coordinated by oxygen atoms of the polyani­ons, the others form a cluster of four face-sharing sodium-oxygen-octahedra. The resulting microporous network contains large hexagonal channels.

The binuclear antimony(V) complexes Cl 3 Sb(0)[R 3 (R 1 O)PO 2 ](OR 2 )SbCl 3 with R 1 = R 2 = CH 3 and R 3 = p-ClC 6 H 4 CH 2 (1), p-O 2 NC 6 H 4 CH 2 (2) are prepared by reaction of the corre­sponding benzylmethoxophosphonic acids with antimony(v) chloride, water and methanol. 2 crystallizes in the orthorhombic space group Pnma with a = 1297.3. b = 1324.8, c = 1269.7 pm and Z = 4. The molecules of 1 and 2 are formed from two octahedra sharing one edge with antimony central atoms. Oxygen atoms are the links between the antimony atoms which are bridged by the bidentate phosphonato ligand. In solution the bridging phosphonato groups are inverted rapidly and the R 2 groups undergo a slow intermolecular exchange. Two isomers can be detected by NMR spectroscopy.

Perchlorinated derivatives of the common o-diimine chelate ligands 2,2′-bipyridine and 1,10- phenanthroline were synthesized and tested for their coordination behavior towards metal ions. Octachloro-1,10-phenanthroline (ocp) was obtained via chlorination with PCl 5 under pressure (300 ° C, 18 h). It fails to form stable complexes with e.g. Fe 2+ , Mn 2+ , Ru 2+ , Ni 2+ . Zn 2+ or Cd 2+ , but yields complex cations [M(ocp) 2 ] + with M = Cu, Ag. The crystal structure analy­sis of the red tetrafluoroborate of the copper(I) complex cation reveals a distorted tetrahedral coordination at the metal with a slight tendency towards the trigonal-pyramidal arrangement; two essentially planar ligands with small bite angles intersect at almost right angle. Relative to conventional bis(1,10-phenanthroline)copper(I) complexes with similar structures. [Cu(ocp) 2 ] + has oxidation and reduction potentials shifted positively by about 1 V which leaves the energy of the main MLCT absorption features little changed. Attempts to synthesize RuCl 2 (ocp) 2 in DMF produced as substituted product a symmetrical bis(dimethylamino)-hexachloro-1,10-phenanthroline which can be oxidized electrochemically in two steps. In contrast to ocp, octachloro-2,2′-bipyridine (ocb) showed no detectable complexation with Cu + and a very neg­ative reduction potential, most probably due to its inability to exhibit a low-energy coplanar conformation.

A series of diamagnetic macrocyclic nickel complexes I bearing substituted dibenzotetraaza[14] annulene ligands with methyl and/or phenyl groups on NCR moieties and methyl or nitro groups on the phenylen units have been prepared by Ni template synthesis from the correspon­ding 1,3-diketo- and 1,2-diamino-benzene components. 1 H and 13 C NMR data are reported and interpreted in terms of sterical and electronical changes induced by these substituents upon the ligand and compared with results of theoretical calculations. Further characterisation is based on IR, UV/Vis and mass spectroscopic measurements.

Two forms of the new compound Pd(py) 4 I 6 have been prepared by the reaction of stoichiome­tric amounts of PdCl 2 , C 5 H 5 N, KI and I 2 in water. One modification crystallizes triclinically in space group Ρ1̄ with a = 907.7(3), b = 960.5(7), c = 992.0(4) pm, α = 117.31 (4), β = 103.35(3), γ = 86.01(5)° and Z = 1, the other orthorhombically in space group Pnnm with a = 891.6(4), b = 1047.6(4), c = 1659.1(5) pm and Z = 2. Both structures may be described as layerlike packings of I 3 - anions and [Pd(py) 4 ] 2+ cations. Differences arise from the orientations of the anions and cations within these layers. The new compond Pd(py) 2 l 6 has been prepared by recrystallisation of Pd(py) 4 I 6 from chlo­roform. It crystallizes in the monoclinic space group I2/a with a = 1801.1(4), b = 584.0(1), c = 2220.5(6) pm, β = 115.78(2)° and Z = 2. The structure is built up from quasi square planar complexes [Pd(py) 2 l 2 ] and iodine molecules I 2 linked together to give alternating screw- and zigzag-shaped chains ^[I _ -I 2 ] along [1 0 01 forming nets of type (10, 3) including the Pd 2+ ions. The structure may also be described as a layerlike packing of the anionic chains 1 ∞ [I - · I 2 ] and linear complex cations [Pd(py) 2 ] 2+ parallel [0 1 1].

The new compound [K(Crypt-2.2.2)]I(ICN) 2 has been prepared by the reaction of [K(Crypt- 2.2.2)]I with excess ICN in Ethanol. It crystallizes in the triclinic space group Ρ1̄ with a = I 192.3(2), b = 1197.2(2), c = 1278.1(3) pm, α = 69.79(2), β = 72.67(2), γ = 75.79(1)° and Z = 2. The crystal structure has been refined to R F = 0.032 for 3857 reflections.The structure may be described as a layerlike packing of polypseudohalide anions I(ICN) 2 - and of complex cations [K(Crypt-2.2.2)] + .

XeF 2 and H 2 O react with [C 6 F 5 Xe] + [AsF 6 ] - in HF without Xe-C bond cleavage under formation of the cyclohexadienone compound [3-O-1.4-CeF 5 Xe] + [ AsF 6 ] - The FC=CF moiety in this dienone is epoxidised with the same reagent. The cyclohexadiene compound [1,4-C 6 F 7 Xe] + [AsF 6 ] - could also be epoxidised under the same conditions.

Electrophilic oxygenation of polyfluorobenzenes C 6 F 5 X (X = F. Cl. Br. H, CF 3 , NH 3 + , NMe 3 + , OH and OCH 2 CF 3 ) with XeF 2 and H 2 O in HF leads to the formation of polyfluorinated 1,4- cyclohexadienones. Pentafluoroiodobenzene is converted into C 6 F 5 IF 2 and C 6 F 5 IF 4 , whereas [CeF 5 N 2 ] + [NbF 6 ] - is unreactive towards this new type of electrophilic oxygenation.

Reductive condensation of Ph 3 P=C(SiMe 3 ) 2 and PCl 3 or PBr 3 yields the ionic halides of the 3,5-bis(triphenylphosphonio)-1,2,4-triphospholide cation 5. The compounds can take up two moles of halogen X 2 . In the first step bis(triphenylphosphoranediyl)trihalo-1,2,4-triphos- pholanes 6 are formed. Low temperature 31 P NMR spectroscopy shows them to exist in two conformeric forms. In polar solvents heterolytic dissociation of the phosphorus-halogen bond in the 4-position occurs. The molecular structure of 5 demonstrates a cyclic delocalized bonding system. Chlorination or bromination (to give 6) effects little structural change with exception of a large increase of the PP bond length. The phosphorus-halogen bonds in 6 are very long and rather different in length. The overall situation as well as the structural details can be rationalized to result from a negative hyperconjugation between the ylidic carbon atoms and the phosphorus-halogen bonds.

A compound MgX 2 ·2AsX 3 · 5THF (X = Cl, Br) has first been obtained by chance during an attempt to prepare mesitylarsenic dichloride from AsCl 3 and mesitylmagnesium bromide. Then, MgCl 2 · 2AsCl 3 · 5THF was synthesized from the components. X-ray crystallography revealed that this compound is best described as [trans-MgCl 2 (THF) 4 )]·(2AsCl 3 · THF). The AsCl 3 units are weakly interacting with the Cl atoms of the MgCl 2 (THF) 4 molecules, while the fifth THF molecule interacts with both AsCl 3 units making the As atoms hexacoordinated. This arrangement generates a chain structure in the orthorhombic lattic.

Single crystals of Ba 0,5 Bi 0,9 V 8 O 16 , have been prepared with CO 2 -LASER techniques. The compound crystallizes with tetragonal symmetry, space group C 4h 5 - I4/m. a = 9.943(2). c = 2.893(2) Å. Z = 1 and belongs to the Hollandite family. The two different tunnel positions are occupied by Ba 2+ and Bi 2+ . As a result of this Ba 2+ shows a cuboctahedral and Bi 3+ a square pyramidal BiO 4+s 2 coordination if the lone pair of bismuth is included.

The reaction of [Fe(NiSiMe 3 ) 2 ) 2 ] with thiols RSH, elemental sulfur, and neutral ligands L (with sulfur donor atoms, e. g. thiourea derivatives) gives [Fe 4 S 4 (SR) 2 L 2 ] clusters in high yields. The structure of [Fe 4 S 4 (2.4.6-(C 3 H 7 ) 3 C 6 H 2 -S) 2 (dpdmi) 2 ] (dpdmi: diisopropyldimethyl- imidazolthion) was determined by X-ray crystallography. When [Fe 4 S 4 I 4 ] 2- is reacted with a large excess of PMePh 2 or PMe 2 Ph [F 6 S 6 I 2 (PMePh 2 ) 4 ] and [Fe 6 S 6 l2(PMe 2 Ph) 4 ]. respectively, are obtained in nearly quantitative yield. Basket-like structures of the [Fe 6 S 6 ] 2+ cores were detected by X-ray structure analysis. While [Fe 4 S 4 (SR) 4 ] 2- clusters do not react with phosphanes at ambient temperature 2:2 functional­ized species like [Fe 4 S 4 (SR) 2 (tmtu) 2 ] lead to basket-type clusters [Fe 6 S 6 (SR) 2 (PR 3 ) 4 ].

[MoCl 4 (Ph-C≡C-Se-C 4 H 9 )(SEt 2 )] has been prepared by the reaction of trans-[MoCl 4 (SEt 2 ) 2 ] with Ph-C≡C-Se-C 4 H 9 in dichloromethane solution. The complex was characterized by IR spectroscopy and by a crystal structure determination. Space group P2 1 /c. Z = 4. structure solution with 4595 independent reflections. R = 0.057 for reflections with I > 2σ(I). Lattice dimensions at -65°C: a = 1002.8(2). b = 730.74(5), c = 2703.1(7) pm. β = 95.78(1)°. The complex has a molecular structure in which the molybdenum atom is seven-coordinate by four chlorine ligands, by the two alkyne carbon atoms, and in irons position to the latter by the sulfur atom of the thioether molecule. The MoC bond lengths of 190.2 and 200.9 pm are surprisingly different.

The structures of 1,6-diamino-1,6-diphenyl-1,3,5-hexatriene (2) and its 1,6-bis(N.N-bistrimethylsilylamino)-derivative (3) are compared. The X-ray crystal structure analyses of 2 and 3 show that turning off the conjugation with the nitrogen lone pairs by orthogonal orientation of the R 2 N-plane has no measurable effect on the structural features of the framework of the central planar carbon π-system. In a related substituent-stabilized primary enaminc (4) a slightly elongated C=C bond is found by X-ray diffraction.