Bis(cyclopentadienyl)titanium complexes of naphthalene-1,8-dithiolates, biphenyl 2,2'-dithiolates, and related ligands

Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The pro-ligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp(2)TiS(2)Ar complexes (Ar = naphthalene) have been shown by temperature-dependent (1)H NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS(2)C(3) rings undergoing inversion on the NMR time scale while the similar Cp(2)TiS(2)Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO(2) groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported.     

Steric mode of enzymic hydroxylation at primary carbon atoms: Hydroxylation of (1R)- and (1S)-[1-3H, 2H, 1H][1-14C]-octanes by Pseudomonas Oleovorans

(1R)- and (1S) [1-³H, ²H, ¹H]-octanes and mixed with [1-¹⁴C]-octane, were synthesized. The mixed samples were incubated with homogenats of P. oleovorans strain TF4-1L and the biosynthesized mixtures of octanols isolated. It was shown that mainly the achiral termini [-C¹H₃] were hydroxylated and that chiral methyls were oxygenated to the extent of 20–30%. In all instances the products derived from hydroxylation at the chiral methyls [-C-³H, ²H, ¹H] were mixtures of (1R)- and (1S)-octanols, the major component of which was the alcohol obtained by displacement of ¹H. The results indicate that hydroxylation proceeded with a normal isotope effect k_h>k_d>k_t. The amount of (1R)-octanol in the mixtures of octanols derived from (1R)- and (1S)-octane was determined. It was found that the C-1 hydroxylation of octane proceeded with retention, i.e. the incoming hydroxyl assumed the orientation of the displaced hydrogen (or isotopic hydrogen) atom.     

Unbiased expectation values from diffusion quantum Monte Carlo simulations with a fixed number of walkers

We append forward walking to a diffusion Monte Carlo algorithm which maintains a fixed number of walkers. This removes the importance sampling bias of expectation values of operators which do not commute with the Hamiltonian. We demonstrate the effectiveness of this approach by employing three importance sampling functions for the hydrogen atom ground state, two very crude. We estimate moments of the electron-nuclear distance, static polarizabilities, and high-order hyperpolarizabilites up to the fourth power in the electric field, where no use is made of the finite field approximation. The results agree with the analytical values, with a statistical error which increases substantially with decreasing overlap of the guiding function with the exact wave function.     

A unique cyanide-bridged three-dimensional (3-D) copper(II)-copper(I) mixed-valence polymer containing 1-D water tapes with cyclic pentamer units

A unique cyano-bridged copper(II)-copper(I) mixed-valence polymer, {[Cu(3)(CN)(4)(H(2)O)(3)](H(2)O)(2)}(n) (1), has been prepared and structurally determined by X-ray diffraction. The cyanide anions with (mu(2),eta(2)) and (mu(3),eta(2)) bridging modes connect the copper centers into a complicated zeolite-like 3-D network. Of further interest, coordinated and lattice water molecules in this structure form 1-D hydrogen-bonded water tapes consisting of linked cyclic pentamer clusters.     

First organophosphorus radical-mediated cyclisations to afford medium-sized rings: eight-membered lactones and seven- and eight-membered lactams

The phosphorus based radical precursors N-ethylpiperidine hypophosphite (EPHP) and diethylphosphine oxide (DEPO) are efficient reagents for carrying out the formation of seven- and eight-membered rings. Esters and amides were successfully converted into the corresponding eight-membered lactones and seven- and eight-membered lactams in good to excellent yields.     

Nonlocality as a feature of the physical world

Aprediction puzzle leads to a form ofnecessary realism which forces the rejection of a central tenet of the Copenhagen interpretation. This leads to reconsidering conceptual difficulties related to Bell's locality premise. It is shown that aparadox of elementary probability theory puts new light on Bell's assumption that causality and statistical independence are mutually incompatible. Nemo dat quod non habet : No one can offer more than he has ability to give; in that spirit, this paper is dedicated to the memory of J.S. Bell.     

Perturbation theory for kinds

In this paper we prove the validity of formal asymptotic results on perturbation theory for kind solutions of the sine-Gordon equation, originally obtained by McLaughlin and Scott. We prove that for appropriate perturbations, of size in an appropriate norm, slowly varying in time in the rest frame of the kink, the shape of the kink is unaltered in theL norm toO() for a time ofO(1/). The kink parameters, which represent its velocity and centre, evolve slowly in time in the way predicted by the asymptotics. The method of proof uses an orthogonal decomposition of the solution into an oscillatory part and a one-dimensional zero-mode term. The slow evolution of the kink parameters is chosen so as to suppress secular evolution of the zero-mode.Partially supported as a graduate student at Princeton University of NSF grant 215 6211     

The microwave spectrum of thioformaldehyde,CD2S,and CH2S: Average structure,dipole moments,and 33S quadrupole coupling

Microwave transitions up to J = 53 in the ground vibrational state of deuterothioformaldehyde, CD₂S, were studied between 8 and 40 GHz. A detailed centrifugal distortion analysis yields accurate constants for comparison with force field values. The isotopic species ¹³CH₂S, CH₂³⁴S, CH₂³³S, ¹³CD₂S, CD₂³⁴S, and CD₂³³S were studied in natural abundance. Accurate average zero-point structures were determined for both CD₂S and CH₂S:

$\text{CH}{}_2\text{S}\text{CS}\text{=1.6138(4)}\text{CH}\text{= 1.0962(6)}\text{A}\text{?}\text{∠}\text{HCH}\text{=116° 16(6)′,}\text{CD}{}_2\text{S}\text{CS}\text{=1.6136(4)}\text{CD}\text{= 1.0931(4)}\text{A}\text{?}\text{∠}\text{DCD}\text{=116° 25(5)′}$

Changes in the zero-point geometry for deuterium substitution were established. Quadrupole fine structure arising from the ³³S nucleus has been measured in CH₂³³S and CD₂³³S. Analysis gives the following coupling constants (for both molecules) as χ_aa = ?11.7 and χ_bb - χ_cc = 88.1 MHz. The dipole moment of CD₂S was measured to be 1.6588(8)D and an accurate comparison with CH₂S was made; the ratio of dipole moments $\text{CD}{}_2\text{S}\text{CH}{}_2\text{S}$ was found to be 1.0062(4). The spectroscopic and bonding properties of CH₂S will be compared with formaldehyde and other molecules.     

Nonclassical titanocene silyl hydrides

The titanocene silyl hydride complexes [Ti(Cp)2(PMe3)(H)(SiR3)] [SiR3=SiMePhCl (6), SiPh2Cl (7), SiMeCl2 (8), SiCl3 (9)] were prepared by HSiR3 addition to [Ti(Cp)2(PMe3)2] and were studied by NMR and IR spectroscopy, X-ray diffraction (for 6, 8, and 9), and DFT calculations. Spectroscopic and structural data established that these complexes exhibit nonclassical Ti-H-Si-Cl interligand hypervalent interactions. In particular, the observation of silicon-hydride coupling constants J(Si,H) in 6-9 in the range 22-40 Hz, the signs of which we found to be negative for 8 and 9, is conclusive evidence of the presence of a direct Si-H bond. The analogous reaction of [Ti(Cp)2(PMe3)2] with HSi(OEt)3 does not afford the expected classical silyl hydride complex [Ti(Cp)2(PMe3)(H)[Si(OEt)3]], and instead NMR-silent titanium (apparently TiIII) complex(es) and the silane redistribution product Si(OEt)4 are formed. The structural data and DFT calculations for the compounds [Ti(Cp)2(PMe3)(H)(SiR3)] show that the strength of interligand hypervalent interactions in the chlorosilyl complexes decreases as the number of chloro groups on silicon increases. However, in the absence of an Si-bound electron-withdrawing group trans to the Si-H moiety, a silane sigma complex is formed, characterized by a long Ti-Si bond of 2.658 A and short Si-H contact of 1.840 A in the model complex [Ti(Cp)2(PMe3)(H)(SiMe3)]. Both the silane sigma complexes and silyl hydride complexes with interligand hypervalent interactions exhibit bond paths between the silicon and hydride atoms in Atoms in Molecules (AIM) studies. To date a classical titanocene phosphane silyl hydride complex without any Si-H interaction has not been observed, and therefore titanocene silyl hydrides are, depending on the nature of the R groups on Si, either silane sigma complexes or compounds with an interligand hypervalent interaction.     

Bis(fluoroalkyl)acrylic and methacrylic phosphate monomers, their polymers and some of their properties

Ten fluoromonomers of structure (R_FO)₂P(O)OCH₂CH₂OC(O)CRCH₂ were made in 30-64% yield by treating the chloridates (R_FO)₂P(O)Cl with HOCH₂CH₂OC(O)CRCH₂ in chloroform in the presence of triethylamine [R_F=CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂, C₄F₉CH₂, C₄F₉CH₂CH₂ or C₆F₁₃CH₂CH₂; R  H or Me]. The chloromonomer (CCl₃CH₂O)₂P(O)OCH₂CH₂OC(O)CHCH₂ was obtained analogously in 29% yield. Polymerisation of the acrylate monomers, but not the methacrylate monomers, could be effected using α-azoisobutyronitrile as a radical initiator. Acrylic polymers having CF₃CH₂O, CCl₃CH₂O and C₆F₁₃CH₂CH₂O side-chains were obtained as translucent rubbers. Specimens of cotton fabric were treated with solutions of the polymers, and average water and oil repellency ratings measured. Fabric coated with the polymer with the C₆F₁₃CH₂CH₂O side-chain afforded protection from penetration of the test liquids. Treated fabrics were subjected to the limiting oxygen index (LOI) test according to BS EN ISO 4589-2 (1999): this test determines the point at which a material just burns in a volumetric flow of oxygen and nitrogen. The treated fabrics were more fire-resistant (LOI 22-29%) than the untreated fabric (LOI 18%). Fabric coated with the CCl₃CH₂O-based polymer can be considered fire-retardant (LOI 29%). The fluoromonomers were tested for anti-acetylcholinesterase activity and were found to be poor enzyme inhibitors; they are predicted to possess low acute toxicity.