Volume 48, Issue 5

Colourless single crystals of Na 2 TiOS 2 were obtained by a fusion reaction of a stoichiometric mixture of Na 2 S, Na 2 SO 3 , titanium-powder and elemental sulphur. Na 2 TiOS 2 is monoclinic, space group P2 1 /c with a = 6.861(3), b = 13.610(9), c = 5.733(9) Å, β = 113.24(2)°, Ζ = 4. The crystal structure (R = 0.032, 811 observations, 55 variables) is characterized by infinite anionic chains of TiO 2 S 2 -tetrahedra sharing the oxygen atoms (d̄ Ti-o = 1.842 Å, d̄ Ti-s = 2.227 Å, Ti—O—Ti = 134.3°). The chains are separated from each other by octahedrally coordinated Na + ions. The structure may be considered as a quaternary variant of the Na 2 GeS 3 -structure type.

The syntheses of tetranuclear complexes Mo,W 2 S 4 L 6 3 and Mo 2 Co 2 S 4 L 2 (CO) 2 (CH 3 CN) 2 4 (L = R 2 PS 2 ⁻; a: R = Et, b: R = Pr) containing the cubane-type Mo 2 M 2 S 4 core are reported. While in 4 both Mo atoms are chelated by L, the dithiophosphinato group acts as a chelating and bridging ligand in 3. It is shown that there exist four isomers of 3 which differ not only in the function of L but also in the kind of metals which are chelated and bridged. Magnetic and NMR spectroscopic data are given. The structure of a mixed crystal of the two β-isomers of 3a containing three bridging and three chelating ligands L is reported: orthorhombic space group Pbca, Z = 8, and lattice parameters a = 2186.6(7), b = 2264.0(7), and c = 2386.7(6) pm.

The title compound crystallizes orthorhombically (space group C 222 1 ) with a = 797.0, b = 870.3 and c = 2739.0 pm. The anions are zwitterions which are heavily involved in intra- and intermolecular NH •••O and OH•••O hydrogen bonding. The two types of sodium cations are coordinated by six oxygen atoms each of which belongs to either SO 3 groups (Na 2) or water molecules and SO 3 groups (Na1). A second type of water molecules is not coordinated to the cations. The SS bond length is 208.2 pm. Infrared and Raman spectra of the title compound are reported and tentatively assigned. The SS stretching vibration is observed at 409 cm -1 .

Lutidines react with Na/K alloy and diorganylaminodifluoroboranes in n-hexane. The products formed depend upon the position of the methyl groups. While from 3,4-lutidine (C) the bis(lutidinyl)aminoboranes 2 - 5 are obtained, the 2,4-, 2,5-, and 3,5-lutidines (F, G, H) give the 11 a, 1 lb-dihydro-[1,3,2]-diazoborolo-[5,l-b;3,4-b']-dilutidines 11-17. 4-Picoline reacts analogously to give 10. Pyridine (A) and collidine (B) give adducts with borane. From 2,3-lutidine (D), the 1,4-dihydro-l,4-bis(fluoraminoboryl)-2,3-lutidine 8 is obtained. 1 H, 11 B, 13 C, 19 F, 29 Si, 15 N NMR and MS data are given. For 8 and 14 the X-ray structures are reported.

The melting diagrams of the systems benzene-HCl, toluene-HCl and mesitylene-HCl have been established and the crystal structures of two adducts determined. The adduct toluene · 2 HCl, melting incongruently at -115°C, is monoclinic with space group C2/c and Ζ = 4 formula units per unit cell; the adduct mesitylene · HCl, m. p. -64°C, is orthorhombic with space group Pbca and Ζ = 8. The HCl molecules are situated on both sides and one side, respectively, of the plane of the aromatic system and are linked to it by weak hydrogen bonds of the type Cl-H···π.

Intermolecular activation of carbon-hydrogen bonds has been accomplished by reduction with sodium amalgam of (sip 3 )(Me 3 P)RuCl 2 , 1, [“sip 3 ” = MeSi(CH 2 PMe) 2 ) 3 ] in aromatic hydrocarbons, such as benzene and substituted derivatives thereof. In these reactions, the 16e equivalent (sip 3 XMe 3 P)Ru(O) thus generated exhibits a preference for insertion across the unhindered metaand para-C-H bonds to produce complexes of composition (sip 3 )(Me 3 P)RuH(C 6 H 3 RR′) [R = R′ = H, 2; R = H, R′ = CH 3 , 3; R = R′ = CH 3 (3,4-xylyl), 4; R = R′ = CH 3 (3,5-xylyl), 5; R = H, R′ = CF 3 , 6], of which 3, 4, and 6 were isolated as mixtures of meta/para-isomers and Ru-aryl rotamers, respectively. Reaction of the phenyl hydride 2 with 4-MeC 6 H 4 NCE (E = O, S) leads to insertion of the heteroallenes into the Ru-Η bond to give (sip 3 )(Me 3 P)Ru[N(C 6 H 4 Me-4)C(O)H]C 6 H 5 , 8, and (sip 3 )(Me 3 P)Ru[SC(=NC 6 H 4 Me-4)H]C 6 H 5 , 10, as the primary products. While the latter forms (sip 3 ), 11, by loss of PMe 3 , the former reacts with another molecule of isocyanate to afford the acyl compound (sip 3 )9, as the ultimate product. Treatment of 2 with CO 2 results in the formation of a carbonato derivative, (sip 3 )(Me 3 P)Ru(O 2 CO), 7. •

Chiral Cyclopentadienyl Complexes, Crystal Structure The reaction of [C 5 Cl 4 (SMe)]Mn(CO) 3 (la) with n-butyllithium and the electrophiles SiMe 3 Cl, CO 2 , or PPh 2 Cl regiospecifically yields the chiral 1,3-disubstituted functional cymantrene thioethers [C 5 Cl 3 (SMe)R]Mn(CO) 3 (R = SiMe 3 (2), COOLi (3a), PPh 2 (4)). 3 a can be protonated to give the corresponding carboxylic acid (3b), which in turn can be transformed to the acid chloride [C 5 Cl 3 (SMe)(COCl)]Mn(CO) 3 (3c). 3c reacts with NaN 3 to yield after work-up the urea derivative OC[[NH—C 5 Cl 3 (SMe)]Mn(CO) 3 ] 2 (3d). Using the cymantrene bisthioethers [C 5 Cl 3 (SR) 2 ]Mn(CO) 3 (R = Me, 5a, Ph, 5b) as starting materials, the carboxyl derivatives [C 5 Cl 2 (SMe) 2 (COR)]Mn(CO) 3 (R = OLi, 6a, OH, 6b, Cl, 6c) and the potential organometallic S,P-chelate ligands [C 5 Cl 2 (SR) 2 (PPh 2 )]Mn(CO) 3 (R = Me, 7a, Ph, 7b) can be obtained. The crystal structure determination of 7a (C 22 H 16 O 3 PS 2 Cl 2 Mn, monoclinic, P 2 1 /c, a = 18.714(6) A, b = 9.506(3) A, c = 14.475(3) Α, β = 109.18(2)°, V = 2432.1(12) Α 3 , Z = 4) shows an orientation of the neighbouring PPh 2 - and SMe groups, that allows chelation of an additional metal fragment.

The reactions of Mn(CF 3 COO) 2 (1) with Ν,Ν,N′,N′-tetramethylethylenediamine (tmen), 2,2′-bipyridine (bipy) and triethanolamine (tea) yield three new mononuclear coordination compounds: trans-[Mn(tmen) 2 (CF 3 COO) 2 ] (2), cis-[Mn(bipy) 2 (CF 3 COO) 2 ] (3), and [Mn(tea)2](CF 3 COO) 2 (4). The X-ray structures of the compounds 2, 3, and 4 are described. The seven-coordination of the manganese(II) ion in 4, as well as the inequivalency of the two tea molecules coordinated to Mn(II) make this compound unique.

By reaction of Cs 2 [B 6 H 6 ] with in situ generated dicyanogen in aqueous alkaline solution the monocyanohydrohexaborate Cs 2 [B 6 H 5 (CN)] and the dicyanohydrohexaborate cis-Cs 2 [B 6 H 4 (CN)2] are formed. The compounds have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of Cs 2 [B 6 H 5 (CN)] was determined from single crystal X-ray diffraction analysis; monoclinic, space group P2 1 /a with a = 9.540(8), b = 9.977(3), c = 10.578(2)Å, β = 105.06(2)°. The B 6 octahedron is compressed in the direction of the nearly linear B—CN bond by about 5%, with bond lengths between 1.71 and 1.76Å. The "B NMR spectra of the two compounds reveal the features of substituted B 6 cages with C 4v and C 2v point symmetry. In the 13 C NMR spectrum of Cs 2 [B 6 H 5 (CN)] a quartet at -139 ppm with 1 J(C,B) 92 Hz is observed. The IR and Raman spectra exhibit very strong CN stretching bands for Cs 2 [B 6 H 5 (CN)] at 2149, and for cis-Cs 2 [B 6 H 4 (CN) 2 ] at 2170 cm -1 .

The green insoluble Ti IV compound which is obtained by treating titanocene with HC1 reacts with PhLi to yield the fulvalene-bridged compound [CpTiPh 2 ] 2 (C 10 H g ) 3(Ph). An X-ray structure analysis of 3(Ph) shows, that the Ti atoms are in a trans arrangement with respect to the fulvalene group. Crystal data for 3(Ph) are as follows: C 44 H 38 Ti 2 , orthorhombic, space group P2 1 2, 1 2 1 , with a = 11,385(2), b = 14,510(2), c = 19,489(4) Å, Z = 4. The crystals exhibit enantiomorphism.

Ni(cdt) reacts with t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 in pentane at 20°C to yield brownish crystals of ( t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni(η 2 -C 12 H 18 ) (1). The molecular structure of 1, as established by X-ray crystallography, exhibits a trigonal-planar coordination geometry of the nickel center with a η 2 bonded cdt ligand. In the crystal 1 exists as two enantiomers, which are determined by the leftor right-handed screw axis of the cdt ligand. The cdt ligand in 1 resists most typical displacement reactions but 1 reacts with CO at – 78°C to afford the colorless 18e complex ( t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni(CO) 2 (2). From the reaction of Ni(cod) 2 with t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 yellow needles of ( t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni(η 2 -cod) (3) are obtained. Low temperature NMR spectroscopy established that only one diene C=C bond is coordinated to nickel(0). At higher temperatures a rapid exchange of the coordinated and unbound C=C bonds is induced. When solutions of 3 are kept at 20°C for several days the dinuclear, almost insoluble yellow complex {( t Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni} 2 (μ-η 2 ,η 2 -cod) (4) precipitates. The reaction of Ni(C 2 H 4 ) 3 and t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 affords orange ( t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni(C 2 H 4 ) (5). From Ni(1,5-hexadiene) 2 and t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 in 1,5-hexadiene the yellow-greenish complex ( t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni(η 2 -C 6 H 10 ) (6) is obtained. As for 3, only one diene C=C bond is coordinated to nickel(0), but the structure is fluxional with exchange of the coordinated and unbound C=C bonds (NMR at 20°C). From a solution of 6 in pentane the dinuclear, diastereomeric compounds rac/meso-{( t Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni} 2 (μ-η 2 ,η 2 -C 6 H 10 ) (7a,b) separate in large yellow crystals. In similar reactions the 1,6-heptadiene complexes ( t Bu 2 Bu 2 PC 2 H 4 P t Bu 2 )Ni(η 2 -C 7 H 12 ) (8) and rac/meso-{( t Bu 2 Bu 2 PC 2 H 4 P t Bu 2 )Ni}2(µ-η 2 μ-η 2 ,η 2 -C 7 H 12 ) (9a,b) are also obtained. In 6, 7a,b, 8, and 9a,b the open-chain diene ligands can easily be displaced, e.g., by ethene to afford 5. Thus, complexes 6, 7a,b, 8, 9a, b are the most reactive. These complexes react readily (the ethene derivative 5 also reacts but very slowly) with butadiene to yield large yellow cubes of ( t Bu 2 Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni(η7 2 -C 4 H 6 ) (10), which is also fluxional. The alkene complexes 5, 6, 7a, b, 8, 9a,b, 10 react with ethyne to yield yellow-brownish crystalline ( t Bu 2 t Bu 2 PC 2 H 4 P 4 P'Bu 2 )Ni(C 2 H 2 ) (11).

Compounds of the type CpRu(PPh 3 )(L)(SH) [L = PPh 3 (2), CO (4)] react with N-alkyl and -arylsulfinyl phthalimides 3a-f to give the chiral complexes CpRu(PPh 3 )(L)[S-S(O)-R] (L = PPh 3 , 5a: R = C 4 H 9 ,5b: R = C 12 H 25 ,5d: R = C 18 H 37 ,5e: R = Tol; L = CO, 6a: R = C 4 H 9 ,6b: R = C 12 H 25 ,6c: R = C 16 H 33 ,6d: R = C 18 H 37 ,6f: R = CH 2 Ph). With 6a-c diastereoselectivities of 5:2, with 6d 5:1, and with 6f 10:3, respectively, are observed. The compounds 5,6 are characterized by their spectroscopic data; the X-ray structural determination of u-6f shows a sulfur-sulfur bond length of 208,6 (3) pm, the dihedral angle Ru-S(1)-S(2)-C(25) is 170,8°. Extended Hückel calculations give information about the rotational barrier around the S-S(O) axis.

Starting from MoCl 5 via the intermediates (MeCN) 2 MoCl4 (1) and (THF) 2 MoCl 4 (2) the tripod complex CH 3 C(CH 2 PPh 2 ) 3 MoCl 3 (4) has been synthesized. The yellow cristalline compound 4 has been fully characterized by standard analytical techniques. X-ray-analysis proves the facial coordination of the tripod ligand. To our knowledge 4 is the first Mo(III)-trihalide coordination compound containing three P-donor-ligands in a facial coordination.

The ortho-phenylene compounds ortho-[(XH)(YH)C 6 H 4 ] (XH, YH = NH 2 , SH, OH) react with Co(BF 4 ) 2 •6H 2 O and Tripod (CH 3 C(CH 2 PPh 2 ) 3 ) to give the five-coordinate Co(III) complexes [Tripod-Cobalt-(ortho-(X)(Y)C 6 H 4 )] + (X, Y = NH, O, S), 1-6. The structures of 1—6 have been characterized by X-ray analyses of appropriate salts. The compounds have further been characterized by IR, NMR, UV-VIS and cyclovoltammetric measurements. As a compound analogous to 1—6, but containing the saturated chelate ligand [(S)C 2 H 4 (S)] 2- instead of the conjugated ortho-phenylene type ligands of 1-6, [Tripod-Cobalt-((S)C 2 H 4 (S))] + , 7, has been prepared and fully characterized. It is inferred that the coordination geometries of 1-7 do not strongly depend on conjugative interaction within the chelating ligands.

Salts of the composition [M(N-MeIm) 6 ](SPh) 2 (M = Mn, Ni; N-MeIm = N-methylimidazole) were prepared by dissolution of the metal powders with N-MeIm solutions of Ph 2 S 2 . X-ray crystallographic examination established that these salts indeed feature uncoordinated PhS - . The salts [M(N-McIm) 6 ](SPh) 2 (M = Mn, Ni) react with S 8 to give [M(N-MeIm) 6 ]S 8 via the intermediacy of the perthiolate salts [M(N-MeIm) 6 ](S 2 Ph) 2 .

The synthesis of some monofluorophosphite esters from the appropriate hydroxy compound and PCl 2 F in the presence of a tertiary amine is described. The reaction of 2,2′-dihydroxy-biphenyl with PCl 3 in the presence of triethylamine did not furnish the expected chlorophosphite 9; instead, the bridged bisphosphite ester, 10, was obtained. Reaction of the fluorophosphite ester 8 with 3,5-di-tert-butyl-benzoquinone furnished the spiromonofluorophosphorane 12 in which λ 5 P is part of a five-membered and a seven-membered ring system. Single crystal X-ray diffraction studies were conducted on compounds 2, 10 and 13. In the case of 2, crystallographic 2/m symmetry and short intermolecular P · · · O distances were observed. Compound 10 shows short intramolecular P · · · O contacts. The catechyl phosphate 13, similarly to other dialkylphosphate esters, was found to be a hydrogen-bonded dimer.

The isolation of Juglorubin (2) from cultures of Streptomyces spp., which produce a series of other hydroxynaphthoquinones, is described. 2 is a unique, unusually condensed ionic colorant with the formula C 28 H 17 NaO 11 . The structure of 2 was elucidated by X-ray structure analysis of the acetyl dimethyl derivative 4. Detailled spectral information is given for the previously unknown benzindenylid-quinone molecule, e.g. the assignment of the 13 C NMR signals. 2 is probably formed in a complex reaction from two Juglomycin C units involving a late C—C-bond cleavage.

The crystal structure of LiZnAs has been verified with single crystal X-ray methods. LiZnAs crystallizes in a filled-up zinc blende type of structure (F 43 m, a = 593.9(1) pm, As at site 4a (000); Zn at site 4d (3/4 3/4 3/4); Li at site 4 c (1/4 1/4 1/4); 25 hkl; R = 0.018). As is coordinated by 4 Li and 4 Zn atoms with identical distances of 257.2(1) pm. Li and Zn atoms are tetrahedrally coordinated by As. No indications for a disorder between Li and Zn have been found.

The crystal structure of β-CsReO 4 , the roomtemperature modification of cesium perrhenate, was determined from single-crystal X-ray data as orthorhombic, space group P nma, a = 5.7556(9), b = 5.9964(8), c = 14.310(2) Å and Z = 4. The structure was refined to R = 0.027, R w = 0.023 for 779 absorption-corrected reflections. It represents an orthorhombic distortion of the tetragonal high-temperature phase α-CsReO 4 . The structure of β-CsReO 4 comprises isolated ReO 4 tetrahedra, linked together by Cs ions. The average Re-O distance was found to be 1.714(4) Å.

The crystal structure of CsSO 3 F was determined from single-crystal X-ray data as tetragonal, space group I4,/amd, with a = 5.6317(2), c = 14.1991(9) Å and Z = 4. The structure was refined to R = 0.028,R w = 0.028 for 403 unique reflections. In contrast to the earlier literature CsSO 3 F is not isomorphous with scheelite but with α-CsReO 4 . The structure contains isolated SO 3 F tetrahedra which are linked together by twelvefold coordinated Cs ions. The average S–O,F distance is 1.453(3) Å.

The ionic compound [Si(acac) 3 ][AgCl2] · CH 2 C1 2 , (1) was synthesized by reaction of [Si(acac) 3 ][HCl 2 ] and silver acetate in dichloromethane. A singlecrystal X-ray analysis shows that the cation has an octahedral tris-chelate structure and that the anion is a polymeric chain, composed of edgesharing AgCl 4 tetrahedra.

CH 3 S(H) + SbF 6 - reacts in HF as solvent with Br 2 to form CH 3 S(Br)F + SbF 6 - . The salt is stable below 195 K and has been characterized by vibrational and 1 H and 19 F NMR spectroscopy.