The structure of triphenylgermanium hydroxide

C18H~6GeO, Mr = 320.9, triclinic, Pi, a = 15.408 (6), b = 19.974 (7), c = 23.264 (11) A, a = 107.78 (4), 13 = 1.03.54 (4), y= 101.51 (3) °, V = 6338 (5)/~3, Z = 16, Dx = 1.34 g cm -3, a(Mo Ka) = 0.71073A, /z = 19.1cm-1, F(000)=2624, T= 293 K, R = 0.055 for 6846 observed reflections. The eight independent molecules in the asymmetric unit form two independent O--H...O hydrogen-bonded tetramers with the O atoms in a flattened tetrahedral arrangement [hydrogen-bond distances in the range 2.609 (11) to 2.657 (11)A]. The Ge atoms are tetrahedrally coordinated with mean Gc O 1.791 (7) and Gc C 1.931 (8) A

[8,8-(PPh3)2-9-(OEt)-8,7-RhSB9H9].0.95(CH2Cl2)

9-Ethoxy-8,8-di(triphenylphosphine)-9,10- tz H-8-rhoda-7-thia-nido-undecaborane( l O) dichloromethane solvate, C38Ha4B9OP2RhS.0.95(CH2C12), Mr = 891.7, triclinic, Pi, a = 10.271 (4), b = 11.401 (3), c = 19.426 (4)/~, a = 74.86 (2), 13 = 88.51 (3), y = 83.51 (3) °, V= 2182 (2)/~3, Z= 2, Dx = 1.357 g cm-3, graphite-monochromated Mo Ka radiation, a = 0.71073 A, /z = 6.5 cm-1, F(000) = 912, T= 294 K, R = 0.038 for 3984 observed reflections. The title compound contains an l 1-atom RhSB9 nido-structured cage with Rh and S atoms adjacent in the open RhSB3 face. An ethoxy group is bonded to the B atom adjacent to Rh in the open face with Rh--B9 2.119 (6) and B9--O 1.387 (9)A. The phosphine ligands are bonded to the Rh atom with one Rh--P bond [2.278 (2)A] trans to the S atom and the other [2.417 (1) A] located perpendicular to the open face of the cage

Twisted [(R3P)PdX] groups above dicarbaborane ligands: 4-dimethylsulfido-3-iodo-3-triphenylphosphine-closo-3-pallada-1,2-dicarbadodecaborane and 3-dimethylphenylphosphine-3-chloro-4-dimethylsulfido-closo-3-pallada-1,2-dicarbadodecaborane

The structural analyses of [3-(PPh₃)-3-I-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀] or [Pd(C₄H₁₆B₉S)I(C₁₈H₁₅P)], (I), and [3-(PPhMe₂)-3-Cl-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀] or [Pd(C₄H₁₆B₉S)Cl(C₈H₁₁P)], (II), show that in comparison with [3-(PR₃)2-closo-3,1,2-PdC₂B₉H₁₁] the presence of the 4-SMe₂ group causes the [PdX(PR₃)] unit (X = halogen) to twist about an axis passing through the Pd atom and the directly opposite B atom of the carbaborane ligand. The halogen atoms are located almost directly above a C atom in the C₂B₃ face, and the conformations of the [PdX(PR₃)] units above the C₂B₃ faces are not those predicted from molecular orbital calculations of the closo-3,1,2-PdC₂B₉ system. The fact that the variation from the predicted conformation is greater in the case of (I) than in (II) may be ascribed to the greater steric interactions induced by the I atom in (I) compared with the Cl atom in (II)

Structure of 1-(3-butynyl)pyridinium p-toluenesulfonate

The 1-(3-butynyl)pyridinium p-toluenesulfonate salt, C9H10N+.CTHTO3S -, contains a C--H...O hydrogen bond between the acetylenic H atom of the cation and a sulfonate O atom of the anion in the solid state [C...O 3.32 (1), H...O 2.49 A, C--H...O 159°]. The X-ray analysis was complicated by disorder in both the cation and anion. A major (85%) and a minor (15%) component of the 1-(3-butynyl)pyridinium cation are present, both occuping the same volume element in the lattice. The methyl H atoms and sulfonate O atoms of the p-toluenesulfonate anion are disordered over two orientations

Synthetic and X-ray diffraction studies of borosiloxane cages [R ' Si(ORBO)(3)SiR '] and the adducts of [(BuSi)-Si-t{O(PhB)O}(3)SiBut] with pyridine or N,N,N ',N '-tetramethylethylenediamine

Eleven borosiloxane [R'Si(ORBO)(3)SiR'] compounds where R-' = Bu-1 and R = Ph (1), 4-PhC6H4 (2), 4-(BuC6H4)-C-t (3), 3-NO2C6H4 (4), 4-CH(O)C6H4 (5), CpFeC5H4 (6), 4-C(O)CH(3)C(6)H4 (7), 4-ClC6H4 (8), 2,4-F2C6H3 (9), and R-' = Cyclo-C6H11 and R = Ph (10), and 4-BrC6H4 (11) have been synthesized and characterized by spectroscopic (IR, NMR), mass spectrometric and, for compounds where R-'= Bu-1 and R = 4-PhC6H4 (2), 4-(BuC6H4)-C-t (3), 3-NO2C6H4 (4), CpFeC5H4 (6) and 2,4-F2C6H3 (9), X-ray diffraction studies. These compounds contain trigonal planar RBO2 and tetrahedral (RSiO3)-Si-' units located around 11-atom &quot;spherical&quot; Si2O6B3 cores. The dimensions of the Si2O6B3 cores in compounds 2, 3, 4, 6 and 9 are remarkably similar. The reaction between [(BuSi)-Si-t{O(PhB)O}(3)SiBut] (1), and excess pyridine yields the 1:1 adduct [(BuSi)-Si-t{O(PhB)O}SiBut]. NC5H2 (12) while the reaction between 1 and N,N,N',N'-tetramethylethy-lenediamine in equimolar amounts affords a 2:1 borosiloxane:amine adduct [(BUSi)-Si-t{O(PhB)O}(3)SiBut](2) center dot Me2NCH2CH2NMe2 (13). Compounds 12 and 13 were characterised with IR and (H-1, C-13 and' B-11) NMR spectroscopies and the structure of the pyridine complex 12 was determined with X-ray techniques. (c) 2006 Elsevier Ltd. All rights reserved.</p

Polyhedral metallathiaborane chemistry. Synthesis and characterisation of metallathiaboranes based on the twelve-vertex icosahedral closo-{MSB10H10} unit, where M is Rh or Ir

The reaction of [nido-7-SB10H12] with [RhCl(PPh3)3] in the presence of N,N,N′N′-tetramethylnaphthalene-1,8-diamine (tmnd) in CH2Cl2 gives twelve-vertex [2,2-(PPh3)2-2-H-closo-2,1-RhSB10H10] (1) and eleven-vertex [8,8-(PPh3)2-nido-8,7-RhSB9H10] (2), as major products, plus the dimeric species [{(PPh3)-closo-RhSB10H10}2] (3) as a minor product. Reaction of 1 with PMe2Ph in CH2Cl2 results in phosphine exchange and hydride substitution, affording the chloro analogue of 1, [2,2-(PMe2Ph)2-2-Cl-closo-2,1-RhSB10H10] (4). By contrast, reaction between [IrCl(PPh3)3] and [nido-7-SB10H12] in CH2Cl2 with tmnd affords only one product, twelve-vertex [2,2-(PPh3)2-2-H-closo-2,1-IrSB10H10] (5). [RhCl2(η5-C5Me5)]2 with [nido-7-SB10H12] under the same conditions gives twelve-vertex [2-(η5-C5Me5)-closo-2,1-RhSB10H10] (6). All the compounds are characterised by NMR spectroscopy, and by mass spectrometry, and the molecular structure of [2,2-(PMe2Ph)2-2-Cl-closo-2,1-RhSB10H10] (4) was established by single-crystal X-ray diffraction analysis. This last rhodathiaborane 4 is fluxional in solution through a process that involves a reversible partial rotation of the {RhCl(PMe2Ph)2} unit above the {SB4} pentagonal face of the {SB10H10} fragment.Contribution No. 113 from the Leeds-Řež Anglo-Czech Polyhedron Collaboration (ACPC). R.M. thanks the Basque Government for a scholarship, and the Ministry of Education and Science of Spain for support within the framework of the “Ramón y Cajal” program. We thank the Ministry of Education of the Czech Republic (project no. LC 523) for support and the UK EPSRC for equipment grants (J/56929, L/49505, M/83360 and R/61949). We also thank the Royal Society (London) and the Czech Academy of Sciences, together with the Royal Society of Chemistry Overseas Author’s fund, for support and assistance with reciprocal visits.Peer reviewe