Volume 49, Issue 6

Na 17 Ga 29 ln 12 (a = 2178.5(5) pm, Fd3m, Z = 8, R = 0.081) and K 17 In 41 (a = 2424.1(5) pm, Fd3m, Z = 8, R = 0.060) have been prepared from the elements and characterized by single crystal X -ray methods. Na 17 Ga 29 ln 12 is a ternary variant of K 17 In 41 . The crystal structure of Na 17 Ga 29 ln 12 contains Ga 12 icosahedra (In 12 icosahedra in K 17 In 41 ) and truncated In 12 tetrahedra which are four-capped and centred by additional Ga atoms (In atoms in K 17 In 41 ). The packing of icosahedra and truncated tetrahedra leads to interpenetrating Samson polyhedra. The Ga 12 icosahedra (In 12 icosahedra in K 17 In 41 ) take the Cu positions of the MgCu 2 type, the In 12 clusters take the positions of the Mg atoms of this structure type. The alkali atoms in Na 17 Ga 29 In 12 and K 17 In 41 occupy the deltahedral faces of the icosahedra and form pentagonal dodecahedra

The preparation of the thiosulfonium salts (CH 3 ) 2 SSSH + SbF 6 - and (CH 3 ) 2 SSSCH 3 + SbCl 6 - from (CH 3 ) 2 SSCl + SbF 6 - and (CH 3 ) 2 SSH + SbCl 6 - , resp., at 195 K is reported. (CH 3 ) 2 SSSH + SbF 6 - is transformed into (CH 3 ) 2 SSSCl + SbF 6 - by reaction with Cl 2 at low temperatures. The salts have been characterized by their Raman spectra

Well-shaped brown and pink isometric crystals were obtained as by-products of the synthesis of erbium selenides from the elements in evacuated and sealed silica ampoules with graphite inlets. They could be identified as erbium seleno mono- and disilicates by energy dispersive X-ray fluorescence and X-ray structure determination. The monosilicate Er 2 SeSiO 4 crystallizes isotypically to Nd 2 SeSiO 4 in the space group Pbcm with the lattice parameters a = 600.2(2), b = 688.0(2), c = 1075.2(2) pm and represents the second known seleno inosilicate of the rare earths. From X-ray structure analysis an isotypic relation between the disilicate Er 3,75 Ca 0,25 Se 2,75 Cl 0,25 Si 2 O 7 and the compound Sm 4 S 3 Si 2 O 7 was found, the former crystallizing in the space group I4 1 /amd with the lattice parameters a - 1177.7(2) and c = 1376.5(2) pm. The doping o f the sorosilicate with the elements Ca and Cl originated from contam inations in the graphit inlets used in the procedure

The formation and the crystal structures of the title compounds are reported. (PhCH 2 NEt 3 ) 4 [Sb 6 l 22 ] and (PhCH 2 NEt 3 ) 4 [Bi 6 I 22 ] are isotypic and contain a novel [E 6 I 22 ] 4- anion (E = Sb, Bi). The anion of (Ph 4 P) 3 [Bi 5 I 18 ] consists of a linear chain of five face-sharing [Bil 6 ] octahedra

The title compounds have been prepared from the elemental components by arc-melting and subsequent annealing. Single crystals of U 3 TiSb 5 and U 3 MnSb 5 were obtained from a tin flux and their structures were determined from single-crystal X-ray data: P6 3 /mcm, Z = 2; a = 913.9(2), c = 611.2(1) pm, R = 0.011 (233 structure factors, 14 variables) for U 3 TiSb 5 and a = 916.8(2), c = 613.2(1) pm, R = 0.015 (427 structure factors, 14 variables) for U 3 MnSb 5 . The lattice constants of the isotypic compounds are: a = 908.2(2), c = 608.3(2) pm for U 3 VSb 5 and a = 911.0(1), c = 611.5(1) pm for U 3 CrSb 5 . The structure of these antimonides may be regarded as an “anti”-type structure of Hf 5 Sn 3 Cu with the antimony atoms on the hafnium sites, while the positions of the uranium and transition metal atoms correspond to the positions of the tin and copper atoms. A comparison of the interatomic distances of U 3 TiSb 5 with those of U 3 Sb 4 , USb 2 , and a-antimony suggests oxidation numbers according to (U +III ) 3 Ti +IV (Sb1 -III ) 3 (Sb2 -II ) 2 , where the Sb2 atoms form weakly bonded chains

The IR and Raman spectra of the ten bromo-iodo-rhenates(IV) [ReBr n I 6-n ] 2- , n = 0 -6 , including the geometrical isomers for n - 2,3,4, have been recorded at 80 K. The vibrational spectra are completely assigned according to point groups O h , D 4h , C 4v , C 3v , and C 2v , as supported by normal coordinate analyses based on a general valence force field. Due to the different mms-influences Br < I in asymmetric axes Br • -Re-I', the Re-I' bonds are strengthened and the Re-Br • bonds are weakened, as indicated by valence force constants, for Re-I' on average 8,5% higher and for Os-Br • 8,3% lower, as compared with the values calculated for symmetric I-Re-I and Br-Re-Br axes, respectively

The isobaric melting and boiling diagrams for the systems: trimethylchlorosilane/pyridine and trimethylchloromethane/pyridine are reproduced. Some measurements of the molar volume of mixtures between trimethylchlorosilane and pyridine and trimethylchloromethane and pyridine are reported. For both systems the molar excess volume has been calculated as a function of the mole fractions

Two isomers of tetrahydro-4,4,8,8-tetramethyl-4,8-disila-s-indacene (LH 2 ) were monodeprotonated and treated with cyclopentadienyl anion and NiBr 2 (THF) 1,5 to give a 72% yield of the mixed nickelocene CpNi(LH) where a cyclopentadiene is fused to a nickelocene. The analysis of the paramagnetic 1 H, 13 C, and 29 Si NMR spectra demonstrated that the syn and anti isomer of CpNi(LH) formed in a ratio of 5/1. Both isomers could be deprotonated to yield the anion CpNi(L - ). According to its 13 C NMR spectrum the bridging ligand L is not planar

The reactions of N-substituted dithiocarbamic acid esters and nickel acetate yield, by partial degradation of the esters, the polynuclear nickel thiolato complexes cyclo-[(μ-SMe) 2 Ni] 6 , 1 and [(μ-SMe) 2 (Ni(MeNHCS 2 )) 2 , 2. Their crystal structures have been determined. The Ni coordination spheres are comprised of four sulfur atoms in a planar arrangement. 1 is a second, highly symmetrical modification of the already known cyclic hexamer Ni 6 (SMe) 12 . In 2 two Ni(PhNHCS 2 ) moieties are bridged to dimers by thiolato groups. Two of these dimers are connected to a tetramer by weak axial Ni-S interactions. Crystal data for 1: monoclinic, space group P2 1 /n, a = 986.1(2), b = 1308.1(3), c = 1228.6(2) pm, β = 96.07(3)°, Z = 2, R = 0.072, R w = 0.062, 3797 reflections. 2: orthorhombic, space group Pnma, a = 1790.0(4), b = 1806.7(4), c = 934.4(2) pm. Z = 4, R = 0.061, R w = 0.051, 2079 reflections

1-Lithiurn-2-hydrogen-1,2-di-tert-butyldiphosphide (1) and 1,2-dilithium-1,2-di-tert-butyldiphosphide (2) have been synthesized by the metalation of 1,2-di-tert-butyldiphosphane with H-butyllithium. 1,2-Dipotassium-1,2-diisopropyldiphosphide (3) and 1,2-dichloro-1,2-diisopropyldiphosphane (4) were obtained by the degradation of a mixture of isopropylcyclophosphanes (i-PrP) 3,4 by potassium and phosphorus(V) chloride, respectively. The compounds 1-4 are easily accessible starting materials for the synthesis of open-chain and cyclic terf-butylor isopropylphosphanes. The 31 P NMR parameters of 1 -4 as well as of the triphosphide K 2 (i-PrP) 3 and the tetraphosphide K 2 (i-PrP) 4 are reported

The luminescence of [SnCl 3 ] - in acetonitrile (τ= 1.6 μs) is quenched by oxygen with k = 3.8x10 8 L mol -1 s -1 . This quenching is associated with an electron transfer from [SnCl 3 ] - in its 3 P 1 sp-excited state to O 2 . Secondary processes lead to the formation of SnOCl 2 (CH 3 CN) n with an overall quantum yield of φ = 1.5 at λ irr = 254 nm. While this Sn(IV) complex is not light sensitive, [SnCl 6 ] 2- in CH 3 CN undergoes a photochemical reductive elimination with the generation of [SnCl 3 ] - with φ - 0.015 at λ irr = 254 nm

The reactions of dendritic amines RN(CH 2 CH 2 CH 2 NH 2 ) 2 (R = Me, c-Hex, PhCH 2 ) and N(CH 2 CH 2 NH 2 ) 3 with tris[(triphenylphosphine)aurio(I)]oxonium tetrafluoroborate [O(AuPPh 3 ) 3 ] + BF 4 - in THF yield species with terminal imido cluster groups -N(AuPPh 3 ) 3 1+ . The compounds have been obtained as stable crystalline solids in high yields and characterized by NMR spectroscopy as well as mass spectrometry and elemental analysis. The triply charged nonanuclear complex [N(CH 2 CH 2 N(AuPPh 3 ) 3 ) 3 ] 3+ exhibits major changes in the 1 H spectroscopic data and in the chemical properties as compared with com pounds with dications [RN(CH 2 CH 2 CH 2 N(AuPPh 3 ) 3 ) 2 ] 2+ (R = Me, c-Hex, PhCH 2 ). Excessive auration to give hypercoordinated species has not been observed

The reaction of methylisatoic anhydride with 2-(aminomethyl)pyridine, 3-(aminomethyl)- pyridine, 3-dimethylamino-1-propylamine, 3-diethylamino-1-propylamine and 3-dibutylamino- 1-propylamine furnished the N-substituted N'-methylanthranilic amides 1-5. In the reaction of 1-5 with phosphorus trichloride the 3-substituted 5,6-benzo-1-m ethyl-1,3,2-diazaphosphorinane- 4-one derivatives 6 to 10 were obtained. The possibility of intramolecular donoracceptor interaction between the nitrogen atom of the R 2 N group and the λ 3 P atom is suggested on the basis of 1 H NMR studies. The reaction of 9 with dimethylamino-trimethylsilane furnished the 2-dimethylamino-substituted product 11. In the reaction of 6, 7 and 10 with bis-(2-chloroethyl)amine hydrochloride/triethylamine the expected substitution products 12 to 14 were obtained. 5,6-Benzo-2-[bis-(2-chloroethyl)amino]-1-methyl-3-(3-picolyl)-1,3,2-diazaphosphorinan- 4-one 13 reacted with (COD)PtCl 2 to give the czs-dichloro-platinum(II) complex 15. The characterisation of 1-15 is based on the 1 H-, 13 C-, and 31 P-NMR spectra, mass spectra and X-ray structure determinations of the precursor compounds 1 and 3

The reaction of adamantane with PCl 3 /A 1 Cl 3 , followed by hydrolysis, gave (1-Ad) 2 P(:O)Cl 1, which was converted to (1-Ad) 2 P(:O)F 2 and (1-Ad) 2 P(:S)Cl 3 by standard procedures. The structure of 1 was confirmed by a single crystal X-ray structure determination; despite the bulky substituents the P-C bond lengths are normal (184.0(3), 185.0(3) pm). Whereas chlorine-fluorine exchange in 3 with AsF 3 furnished (1-Ad) 2 P(:S)F 4, desulfuration of 3 with Ph 3 P to give (1-Ad) 2 PCl 5 failed. The secondary phosphine oxides R 1 R 2 P(:O)H (R 1 , R 2 = 1-Ad: 6; R 1 = 1-Ad, R 2 = t Bu: 7; R 1 , R 2 = t Bu: 8) were synthesized by reaction of 1, 1-AdP(:O)Cl 2 and t BuP(:0)Cl2 with t BuLi. 6 and 8 reacted readily with chloral to give the adducts R 2 P(:O)CH(OH)CCl 3 (R = 1-Ad: 9; R = t Bu: 10). Silylation of 6 with Me 2 NSiMe 3 in the presence of dry air led to (1-Ad) 2 P(:O)OSiMe 3 11, which was hydrolyzed to give (1-Ad) 2 P(:O)OH 12. (1-Ad) 2 POSiMe 3 13 was obtained by the reaction of 6 with n-BuLi, followed by Me 3 SiCl. No reaction took place upon heating 6 with Mo(CO) 6 . (1-Ad) 2 PCl 5 was synthesized in low yield by the reaction of 6 with PCl 3 . The action of tetrachloro-obenzoquinone (TOB) upon 6 furnished (1-Ad) 2 P(:O)(o-OH)C 6 Cl 4 15, whereas the t butyl analogue of 15, 16, was synthesized by hydrolysis of the TOB-adduct of di- t butylfluorophosphine. Analogous 1-adamantyl- and t butyl-phosphorus compounds are compared with regard to their 31 P NMR data

Of the isostructural series of monoclinic (PNP)[Ln(Pc) 2 ]• xH 2 O compounds (Ln = La ••• Tm) the crystal structures of the complex salts of tervalent La (1), Gd (2) and Tm (3) have been determined by single crystal X-ray diffraction analysis. Unit cell data for 2: space group P2 1 /c; a = 15.172(8), b = 20.826(2), c = 25.876(3) Å, β = 95.19(3)°, V - 8143(4) Å 3 , Z = 4; 1 and 3 are isostructural with 2. The lanthanide ion occupies the center of a nearly ideal square antiprism, although the two staggered phthalocyanine rings are severely distorted in an unsymmetrical funnel-shaped fashion due to electronic, steric, and packing influences in the crystal lattice. Steric effects dictate also the geometry of the PNP cation, which adopts a hybrid conformation whose structural characteristics are between the common linear and bent conformers with medium short P-N distances (1.562 Å) and large P-N-P angles in the range 165.6° (1) > 158.3° (2) > 156.1° (3). The strong IR bands at ca. 1375 cm -1 assigned to the asym. (P-N) stretch are diagnostic for this hybrid conformation. The presence of water of crystallization in the periphery of the diphthalocyanine anion is confirmed. The shortest contact distance is observed to one of the bridging nitrogen atoms of the Pc 2- ligand (3.02 Å) indicating a weak (HO-H•••N) hydrogen bond

Paramagnetic [Ni('N Me S 4 ')] 2 1 ('N Me S 4 ' 2- = 2.2'-Bis(2-mercaptophenylthio)diethylmethylamine(2-)) was synthesized from Ni(ac) 2 and Na 2- 'N Me S 4 ' and characterized by X-ray structure analysis. In solid state, 1 contains two pseudo-octahedral [Ni('N Me S 4 ')] fragments bridged via thiolate donors. In contrast to the parent complex [Ni('N H S 4 ')] 2 , the thiolate and thioether donors coordinate cis to the Ni center forming meso [Ni('N Me S 4 ')] fragments of C S symmetry. 1 readily dissociates in solution to give mononuclear [Ni('N Me S 4 ')]. Reaction of [Ni('N Me S 4 ')] 2 1 with PMe 3 yielded [Ni(PMe 3 )('N Me S 4 ')] 2, oxidation by iodine gave the Ni(III) complex [Ni(I)('N Me S 4 ')] 3

The structure of the complex [(η-C 5 H 5 )Ti] 8 (μ-O) 12 has been determined in a crystal of [η-C 5 H 5 )Ti] 8 (μ-O) 12 - 6 CH 3 CN (space group P1̄, Z = 1, lattice dimensions at -4 0 °C: a = 1083.9(3). b = 1292.9(1), c = 1304.0(2) pm, a = 61.18(1)°, β = 71.73(2)°, γ = 70.35(2)°, structure solved using 2164 observed unique reflections, R = 0.043). The Ti atoms occupy the corners of an approximate cube. The 12 oxygen atoms are at the mid point of the edges connecting the Ti atoms. Two pairs of the 12 Ti-O-Ti bridge angles are 147.9(3)° and 148.6(3)°, the remaining eight bridge angles are between 162.4(3)° and 163.9(3)°. The Ti-O distances are between 179.5(5) and 181.8(5) pm with an average of 180.5(5) pm. Each Ti atom is capped by an η 5 -cyclopentadienyl ligand. The same subane-like unit has been found in [(η-C 5 H 5 )Ti] 4 (μ 2 -Se) 3 (μ-Se) 3 -[(η-C 5 H 5 )Ti] 8 (μ 2 -O) 12 Et 3 N THF

The silene Cl 2 Si=C(Ph)CH 2 Bu t (2) is formed by the reaction of 1,1,1-trichloro-2-phenyll- silaprop-2-ene (1) with LiBu t in n-pentane in the temperature range from -15 to 0 °C. The reaction initially leads to the corresponding α-lithio adduct A (addition of LiBu t to the vinyl group of 1); subsequent LiCl elimination yields 2 as an intermediate. 2 can be trapped by Me 3 SiOMe (3) and dienes which add across the Si=C bond. In the absence of trapping agents but in the presence of the Lewis base NEt 3 the mixture 1/LiBu t reacts to give the disilacyclobutane 4. Due to its electronic and steric properties, Cl 2 Si=C(Ph)CH 2 Bu t (2) and butadienes yield mainly the Diels-Alder adducts (5, 7, 9) while with styrene and 1,3-cyclohexadiene the [2+2] and [4+2] products are formed in competition. With 2-norbornene, 2,5-norbornadiene and quadricyclan the [2+2] and [2+2+2] products are formed selectively but only in low yields. In all reactions except with quadricyclan an ene-reaction competes with the cycloaddition leading to ene-compounds as by-products

X-ray crystal structures and properties of the two Pd(II) and Pt(II) complexes [bpeH 2 ][PdCl 4 ] and [Pt(bpe)Cl 2 ], [bpe = 1,2-bis(pyridin-2-yl)ethane] are described and correlated with the IR and 1 H NMR/ 13 C NMR spectroscopic data. In the case of the Pt(II) complex, the 1,2-bis(pyridin-2-yl)ethane is bound to the metal by the heterocycle nitrogen atoms but no direct bond is found in the case of the Pd(II) complex. The ligand exhibits low energy geometries in both compounds: the cis-conformation in the Pt(II) complex, and the transconformation in the Pd(II) complex

The title compounds (natural low-dimensional semiconductors) show strong excitonic optical absorption bands in the UV-visible spectral region, because of the dielectric confinement of excitons. as in the cases of other similar systems based on PbX 2- 4 , SnX 2- 4 . Pt I - X - Pt IV -X , Cd x ,S y -clusters etc

Single crystals of the title complex were fortuitously grown from a dichloromethane solution containing 18-crown-6 and sulfur trioxide. Crystallographic data (at -130 °C): triclinic, space group P1̄, a = 819.1(7). b = 860.6(7), c = 905.8(7) pm. a = 63.98(3), β = 66.56(3), y = 74.95(3)°, V = 0.5236 nm3, Z = 1, D x , = 1.377 Mgm -3 . In the centrosymmetric formula unit, the two CH 2 Cl 2 molecules are situated one above and one below the plane of the ether oxygen atoms. They are C-H···O hydrogen-bonded to two opposing oxygen atoms (H-O 237.1 and 270.6 pm, C-O 335.5 and 365.9 pm, C-H···O 171.7 and 161.8°). The crown ether molecule has approximate D 3d symmetry