87 Matching Results

Search Results

Advanced search parameters have been applied.

Kinetics of Reactions of Substituted Group VI B Metal Carbonyls with Phosphites

Description: The problem with which this investigation is concerned is twofold. The initial part of the problem was to prepare a non-sterically demanding bidentate phosphine ligand, 1,2-bis-(Phosphino)ethane, (P-en), and to determine the kinetics of (P-en)Mo(CO)4 with phosphites via spectrophotometric methods in an attempt to determine if steric effects are directing the type of mechanism followed.
Date: August 1972
Creator: Rettenmaier, Albert J.
Partner: UNT Libraries

Kinetic Study of Ligand Exchange in mu-(2,2,8,8-Tetramethyl-3,7- Dithianonane)-Decacarbonylditungsten(0)

Description: The substitution reaction of (DTN)W2 (CO)10 with P(OCH(CH3 )2 )3 is a stepwise reaction. The kinetics of step 1 follow the equation: -d[substrate] /dt = kld [substrate] + k la [substrate] [ligand]. Thus the mechanism of step 1 is expected to be a competition between dissociative and associative pathways. The kinetics of step 2 follow the equation: -d[(DTN)W(CO)5]/dt = k2dk3[(DTN)W(CO)5][ligand]/k-2[DTN] + k3[ligand] The plot of kobsd versus [ligand] thus is a hyperbolic curve and the plot of 1/kobsd versus 1/[L] exhibits linear behavior. A mechanism for step 2 in which (DTN)W(CO)5 dissociates to an intermediate, W(CO) 5 , and in which DTN and P(OCH(CH3 )2 )3 compete to associate with W(CO) 5 is favored. The dissociative rate constant of the first step, kld' is about 1.2 times of that of the second step, k2d. The dissociation of (DTN)W(CO) 5 from (DTN)W2 (CO) 1 0 is favored over the dissociation of DTN from (DTN)W(CO) 5 due to a combination of the steric, stoichiometric, charge repulsion and entropy effects of the reaction.
Date: May 1982
Creator: Yang, Sang-Nin
Partner: UNT Libraries

The Correlation Between Carbon-Proton and Proton-Proton Coupling Constants

Description: The correlation between the carbon-proton and proton-proton coupling constants have been studied in various 13 systems. Isocrotonic acid-carboxyl-3C, crotonic acid- 13 13 carboxyl-3C, and 5-norbornene-2-carboxylic acid-carboxyl-3C- 1,5,6,7,7-hexachloro were synthesized and their carbonproton coupling constants were analyzed. Nmr studies showed the magnitudes of the carbon-proton coupling constants to correlate well with analogous protonproton coupling constants, although the values of the couplings were larger than expected. The geminal olefinic couplings were considerably larger than all other couplings, but they were self-consistent. The signs of the carbon-proton coupling constants also were in agreement without exception with the signs of analogous proton-proton coupling constants.
Date: December 1975
Creator: Seiwell, Ruth R.
Partner: UNT Libraries

Magnetic Properties of Copper (II) Complexes of Schiff Bases

Description: The synthesis and characterization of two new Schiff base copper(II) complexes are reported. These are Cu(acac: 2-amino-l-phenylethanol) and Cu(acac:2-amino-l-butanol). The ligands, derived from acetylacetone and the appropriate aminoalcohol, are dibasic tridentates with 0,N,O donor atoms. The magnetic properties of the complexes were studied at several temperatures between 78 OK and 296 OK. The magnetic moment of Cu(acac:2-amino-l-phenylethanol) varied little with temperature, and that of Cu(acac:2-amino-lbutanol) increased as the temperature was lowered. This is in contrast to the magnetic moment of Cu(acac:ethanolamine), which decreases as the temperature decreases. Molecular weight data, infrared spectra, magnetic data, electronic spectra, and electron spin resonance spectra of both complexes are reported and discussed.
Date: August 1975
Creator: Jones, William James
Partner: UNT Libraries

Magnetic Properties of Copper (II) Complexes of N-(Hydroxyalkyl) Pyrrole-2-Aldimines

Description: In this work magnetic properties of copper(II) complexes on N-(hydroxyalkyl) pyrrole-2-aldimines were investigated by various techniques, one of which was magnetic susceptibility. Magnetic moments are not directly determined experimentally, but magnetic susceptibilities are.
Date: December 1973
Creator: Pauley, Charles Richard
Partner: UNT Libraries

Kinetic Studies and Vibrational Spectra of Disubstituted Metal Carbonyls

Description: The oxidative elimination reactions of (5-X-phen)Mo(C0)₄ (X = H, CH₃, Cl, NO₂; phen = o-phenanthroline) and (3,4,7,8-(CH₃)₄-phen)Mo(CO)₄ with mercuric chloride in acetone have been investigated. In these reactions, a carbon monoxide group is replaced by two univalent ligands, accompanied by the corresponding increase in coordination number and formal oxidation state of the central metal atom, to give products of the type, (X-phen)Mo(CO)₃(Cl)HgCl. With the exception of (3,4,7,8-(CH₃)₄-phen), the substituted o-phenanthrolines were selected so as to minimize steric differences from one substrate to another while obtaining the widest range of pKₐ of the ligand.
Date: May 1972
Creator: Jernigan, Robert Thorne
Partner: UNT Libraries

Infrared Studies of Group VIB metal Carbonyl Derivatives

Description: With three different proposals for the bonding in metal carbonyls, it was decided to look into the situation more thoroughly in order to see what other evidence was available to support or refute any of these ideas. It became obvious that a definite contradiction existed between the kinetic evidence of various metal carbonyls, and the concept of MC bond strengths as predicted by Cotton's theory.
Date: August 1971
Creator: Brown, Richard Arthur
Partner: UNT Libraries

A Reinvestigation of the Kinetics and Mechanism of Ligand Exchange in Mu-(2,2,8,8-Tetramethyl-3, 7-Dithianonane)-Decacarbonylditungsten(0)

Description: This student is interested in reinvestigating the kinetics and mechanism of the bridged compound in l,2-dichloroethane with triisopropyl phosphite and in finding the reasons why the values of competition ratio k₋₂ /k₃ in this reaction are so large.
Date: August 1988
Creator: Liao, Jing-Piin
Partner: UNT Libraries

Reactivity of Five-Coordinate Intermediates Derived from (Chelate) Tetracarbonylmetal (0) Complexes

Description: The reactivity of the [(Phen)Cr(CO)_3] intermediate with phosphines and phosphites (L) has been investigated through ligand-competition studies. This intermediate possesses virtually no ability to discriminate among L. The agreement between reactivity data for the thermal and photochemically-generated intermediates indicates that the same intermediate is produced via each process. Pulsed laser flash photolysis of (n^2-NP)M(CO)_4 (I) (M = Cr, Mo; NP = 1-diethylamino-2-diphenylphosphinoethane) in the absence and presence of P (OPr-i)_3 (L) in 1,2-dichloroethane and chlorobenzene induces unimolecular ring-opening to afford [(n^1-NP)M(CO)_4] (II), in which the bidentate ligand is coordinated through P. Reaction of this intermediate takes place through competitive ring-reclosure and attack at (II) by L to afford (I) and cis-(n^1-NP) (L)M(CO)_4.
Date: December 1983
Creator: Mansour, Saber E. (Saber El-Sayed)
Partner: UNT Libraries

Synthesis and Characterization of Copper(II) Complexes

Description: A series of dihydroxy bridged copper(II) complexes of the type [(L)Cu(OH)₂Cu(L)]x₂ * nH₂0, where L is 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine or 1,10-phenanthroline, x is a counter ion, and n is the number of water molecules, was synthesized. In the case of monohydroxy bridged copper(II) complexes, we have found a new method of synthesis for [ (L)₂Cu(OH)Cu(L)₂ ] (ClO₄)₃, where L is 2,2'-bipyridine or 1,10-phenanthroline. We have synthesized five new monohydroxy bridged copper(II) complexes, thus increasing the number of monohydroxy bridged copper(II) complexes to nine. All complexes have been characterized by infrared spectroscopy, UV-visible spectroscopy, magnetic moments, and elemental analysis. The electron spin resonance results establish that the fulvic acids contain organic free radicals as an internal part of their molecular structure. The concentration of unpaired electrons will increase by increasing the pH. The unpaired electron in fulvic acid interacts with the unpaired electron on copper(II) through the Π system, and this will decrease the spin concentration of fulvic acid complexed with copper(II). The displacement of titration curve from a free ligand (fructose-1,6-diphosphate, ribulose-1,5-diphosphate, phospherine, phosphothreonine, and 3-phosphoglyceric acid, to a ligand plus copper(II) (1:1 ratio) shows there is a strong interaction between copper(II) and the corresponding ligand. All complexes absorb UV-visible at 250-300 nm. The absorption intensity changes as a function of pH. Copper (II) forms a complex with fructose-1,6-diphosphate, ribulose-1,5-diphosphate, phosphoserine, phosphothreonine, and 3-phosphoglyceric acid by the ratio of 1:3, 1:3, 1:1, 1:1, and 1:2, respectively.
Date: December 1984
Creator: Amani, Saeid
Partner: UNT Libraries

Studies of Solvent Displacement from Solvated Metal Carbonyl Complexes of Chromium, Molybdenum, and Tungsten

Description: Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of Cr.
Date: August 1990
Creator: Zhang, Shulin
Partner: UNT Libraries

Spectroscopic and Physical Effects of Highly Polar Groups

Description: Since the development of the understanding that the electron distribution within a molecule is chiefly responsible for its properties and behavior, factors influencing this charge distribution have been of interest to scientists. The chemical reactivity of a molecule, the physical properties, and to a large extent, structure and geometry, are all functions of the electron distribution. This study examines the issue of electronic structure from two points of view, each of them focussing on a specific component within the molecules studied. In the present work, the effects of the highly polar carbonyl group on spectroscopic parameters and physical behavior are investigated. An additional area of study is the effect of fluorine substitution on the energy levels of some halogenated ethylenes. The specific parameters examined are the ionization potentials, the absorption frequencies, and the energies of a class of excited states known as molecular Rydberg states. It was during the study of these halogenated ethylenes that the observations leading to the carbonyl compound investigations were made, so that the two areas examined are connected both experimentally and chemically.
Date: December 1981
Creator: Schander, Judith Turner
Partner: UNT Libraries

Conformational Analysis Using Carbon-13-Carbon-13 and Carbon-13-Hydrogen Spin-Spin Coupling Constants

Description: This study consists of four major areas of research. First, the relationship between and was extended to Lrl nil homoallylic couplings and was used to determine the relative degree of puckering in a series of dihydroaromatic carboxylic acids. Second, the effect of coupling contributions transmitted through space were examined by theoretical calculations of the intermediate neglect of differential overlap finite perturbation theory type (INDO-FPT) including selective overlap reduction experiments to determine the sign and magnitude of the major through-space contributions and the effect of the orientation of the substituent upon the vicinal carbon3 carbon coupling. Third, the dependence of the J upon substituent orientation in norbornanes was empirically investigated by the synthesis of a series of lactones and cyclic ethers whose conformation was rigid and known. Fourth, a large number of norbornanes substituted with methyls in the 1, 3, and 7 position and a carbon-13 labeled substituent in the 2 position were synthesized and studied in order to obtain a variety of vicinal C-C couplings; all the NMR parameters for this series of compounds were determined while the carbon13 labeled substituent was varied from methyl to methylene to carbinol to aldehyde and to carboxylic acid.
Date: May 1981
Creator: McDaniel, Cato R., Jr.
Partner: UNT Libraries

Ozonolysis and Cycloaddition Reaction of (Trimethylsilyl)ketene

Description: The purpose of this investigation was to study the chemistry of the new and novel (trimethylsilyl)ketene. This ketene was synthesized by pyrolysis of (trimethylsilyl)ethoxyacetylene which was prepared from ethoxyacetylene and methyllithium. (Trimethylsilyl)ketene is a very stable and isolable ketene which does not dimerize and, therefore, provides an opportunity for some unique studies that have not been possible with other monosubstituted ketene.
Date: August 1980
Creator: Saidi, Kazem
Partner: UNT Libraries

Sites of Reactivity During Ligand-Exchange Reactions in Octahedral Group VIB Metal Carbonyls

Description: The site of initial metal-carbonyl bond-breaking during ligand-exchange reactions in a series of octahedral metal carbonyls of the type (L2)M(CO)4 (M = Cr, Mo, W; L2 = diphos, phen, dipy) has been determined employing infrared spectroscopy and Fourier transform nuclear magnetic resonance spectroscopy. The results of this study reveal, for all metal carbonyl complexes of the type mentioned above, that loss of CO occurs exclusively at an axial position (cis to the bidentate ligand, I^)• The dynamic nature of the five-coordinate intermediates, such as (diphos)Mo(CO)3, (phen)M(CO)3 (M = Cr, Mo, W), and (dipy)Cr(CO)3, which are generated in solution upon CO dissociation, is reported and discussed. The results of this investigation confirm that these intermediates are fluxional on the time scale of CO-exchange process. A mechanism which describes the site of initial metal-carbonyl bond-breaking and the fluxionality of the five-coordinate intermediate during ligand-exchange reactions in the complexes (L2)M(CO)4 is proposed. A kinetic study of reactions of W(CO)6 with pseudo-halide anions (NCS-, NCO-, CN-) has been initiated. The results indicate that these reactions proceed via a bimolecular path, which involves initial attack of the pseudo-halide anion at a carbonyl carbon of W(CO)6,
Date: December 1979
Creator: Asali, Khalil Jamil
Partner: UNT Libraries

Electric Dichroism Spectroscopy in the Vacuum Ultraviolet

Description: When a molecule, which possess a permanent dipole moment is exposed to an intense electric field, its absorption spectrum may be altered. These alterations are manifest as shifts in energy and as changes in band shape and intensity. The electric dichroism of absorption bands can be used to probe the excited state that is formed when a molecule undergoes a transition. The properties that may be investigated include transition polarization, excited state dipole moment and mean polarizability, and field-induced mixing of symmetrically equivalent excited states. The theoretical model and experimental devices that have been developed to determine these properties are presented and discussed. The data, taken in total, and its combination with other existing evidence, adds credence to the assignment of the second excited singlet of aldehydes and ketones to be extravalent, accompanied by relatively large delocalization of electronic charge, and polarized in-planiie and perpendicularly to the C-0 axis.
Date: May 1978
Creator: Causley, Gary C.
Partner: UNT Libraries

Some Studies Pertaining to the Biosynthesis and Metabolism of Asparagine and Lysine in Lactobacillus Arabinosus: I. B-Aspartylhydroxamic Acid: Its Action as a Feedback Inhibitor and a Repressor of Asparagine Synthetase in Lactobacillus Arabinosus II. Purification and Properties of Diaminopimelate Decarboxylase from Lactobacillus Arabinosus

Description: That Lactobacillus arabinosus 17-5, ATCC 8014, can supply its own requirement for the amino acid, lysine, is demonstrated by the fact that the organism is capable of growth in media devoid of lysine. Since the final biosynthetic step in lysine formation in all bacteria studied to date involves the decarboxylation of meso-dlaminopimelic acid (DAP) to produce lysine, it was of interest to determine whether an enzyme catalyzing such a reaction (DAP decarboxylase) is present in L. arabinosus.
Date: August 1969
Creator: Chen, Yueh Tsun
Partner: UNT Libraries

Solvent and Ionic Complexes of the Calix[6]arenes

Description: One of the more attractive attributes of calixarenes is their wide variety of possible conformations and hence cavity shapes. However, the flexibility that allows this long-range benefit gives rise to major synthetic challenges when working with the larger members of the family. O-alkylations have proven to be the most widely employed synthetic routes to "functionalization" of the calixarenes, and these have shown a dependence upon both solvent and the metal ions present. Surprisingly, there have been no structural data presented concerning the complexes between the simple unsubstituted calix[6]arenes and the metal ions of groups 1 and 2. The structures of four complexes, containing cesium, rubidium, and calcium are reported as determined by X-ray crystallography. The solution behavior of the complexes for both representative groups is also discussed, in particular with regard to conformational stabilization of the calix[6]arenes and the role of solvent upon this stabilization. These complexes are also investigated as starting materials for the selective functionalization of the calix[6]arenes.
Date: December 1997
Creator: Wolfgong, William J.
Partner: UNT Libraries

Part I: Solid State Studies of Larger Calixarenes : Part II: Synthesis and Characterization of Metallocalixarenes

Description: Calixarenes are a class of macrocyclic compounds that have garnered interest in large part because of their ability to form host-guest complexes with various types of molecules. For all of the studies of complex formation by calixarenes, most of the work to date has concentrated upon the smaller calixarenes, and little is understood about the relationship between the complexes formed when in solution and that observed in the solid state. The first part of the study, presented in Chapter 3, is of the solid-state properties of two of the larger calixarenes, and in comparison to other reported structures reveals patterns to the observed conformations both in the solid state and in solution. The formation of metal complexes has also been investigated and has focused extensively upon the metals as guests. Thus, the ability of the calixarenes to act as ligands in inorganic complexes has been virtually untapped, despite the polyoxo binding site they can easily provide, and very few metallocalixarenes have been reported. The second part of this study goes beyond the simple solid-state properties of such compounds, and involves the synthesis of several metallocalixarenes as part of a project directed at the functionalization of calixarenes with the components of a class of catalysts known to polymerize various olefins. These catalysts, commonly referred to as Ziegler-Natta catalysts, are introduced in Chapter 4. The new compounds presented here--three new aluminocalixarenes in Chapter 5 and a new titanocalixarene in Chapter 6--were synthesized so as to contain some of the same components observed in several of the other catalysts. These new compounds have been characterized crystallographically as well as through proton and multinuclear NMR, and observed conformational patterns are discussed.
Date: May 1998
Creator: Smith, Janna Marie
Partner: UNT Libraries

Part 1. Investigation of Aluminum Amino Acid Complexes; Part 2. Structural Studies of Aluminum Chalcogen Bonds

Description: Five different complexes of aluminum and amino acids have been synthesized and characterized. Reaction between aluminum halides and amino acids that do not contain either a carboxylate or a hydroxy group in the side chain produce complexes of the general formula, [Al(amino acid)_n(halide)_3-n]_m. The most prevalent form of this form of complex is where n = 2, and an example of this in which the halide is replaced by hydroxide ligand has been structurally characterized. The complex for which n = 3 may be obtained by employing a large excess of acid, and that for which n = 1 may be obtained by employing either equimolar conditions or an excess of aluminum halide. Reactions of aluminum halides with amino acids that contain either a carboxylate or hydroxy-containing side chain may result in complexes in which the side-chain is also bound. These proved impossible to characterize fully in the case of aspartic acid. For serine, however, a complex in which the amino acid binds in a chelating fashion through both the carboxylate and hydroxy groups was isolated. It was possible to form complexes when utilizing aluminum alkyls as the metal source. However, these complexes could only be isolated when the reactivity of the species was controlled by the presence of bulky groups. In these cases, the monomeric R_2Al(amino acid) complexes were obtained. Four complexes that contain aluminum-chalcogen bonds were structurally characterized. These included the bulky alkoxide complexes (BHT)_2AIH(OEt_2), (BHT)_3Al(cyclohexanone), and the cubane [(t-amyl)AlS]_4.
Date: May 1996
Creator: Gravelle, Philip W. (Philip Wyn)
Partner: UNT Libraries

Thermal Reactions of Four-Membered Rings Containing Silicon or Germanium

Description: The synthesis of E- and Z-1,1,2,3-tetramethylsilacyclobutanes is described. Pyrolysis of either isomer at 398.2 °C provides the same products but in different amounts: propene, E- and Z-2-butene, allylethyldimethylsilane, dimethylpropylsilane, the respective geometric isomers, 1,1,2,3,3-pentamethyl-1,3-disilacyclobutane, 1,1, l-ethyldimethyl-2,2,2-vinyldimethyl-disilane and E- and Z-1,1,2,3,3,4-hexamethyl-1,3-disilacyclobutane. Mechanisms involving di- and trimethylsilenes are described for disilane formation and rate constants of the elementary steps for the fragmentation reactions are reported. Photochemically generated dimethylsilylene in the hydrocarbon solution inserts into the cyclic Ge-C or Si-C bonds of 1,1-dimethylgerma- or silacyclobutane to produce 1-germa-2-sila- or 1,2-disilacyclopentane. The relative reactivities of 1,1-dimethylgerma- and silacyclobutanes toward the dimethylsilylene have been determined. The carbenoid resulting from the cuprous chloride catalyzed decomposition of diazomethane at 25 °C in cyclohexane reacts with 1,1-dimethylgermacyclobutane to give, surprisingly 1,1,5,5-tetramethyl-1,5-digermacyclooctane as the major product. The reactions of the carbenoid with 1,1-dimethylsilacyclobutane are described. The kinetics of gas phase thermal decomposition of 1,1-dimethylgermacyclobutane has been studied over the temperature range, 684 - 751 K at pressures near 14 Torr. The Arrhenius parameters for the formation of ethylene are k_1 (s^-1) = 10^(14.6 ± 0.3) exp (62.7 ± 2.9 kcal mol^-1/RT) and those for the formation of propene and cyclopropane are k_2 (s^-1) = 10^(14.0 ± 0.1 ) exp (60.4 ± 2.8 kcal mol^-1/RT). Static gas phase pyrolyses of 1,1-dimethyl-lsilacyclobutene, DMSCB, in the presence of a variety of alkenes and alkynes at 260 - 365 °C have been studied. Our experimental results suggest that under these conditions the DMSCB ring opens to 1,1-dimethyl-l-silabutadiene, which either recyclizes to DMSCB or reacts with alkenes or alkynes in competing 4 + 2 and 2 + 2 cycloadditions.
Date: December 1988
Creator: Namavari, Mohammad, 1950-
Partner: UNT Libraries

Detection of the Resonant Vibration of the Cellular Membrane Using Femtosecond Laser Pulses

Description: An optical detection technique is developed to detect and measure the resonant vibration of the cellular membrane. Biological membranes are active components of living cells and play a complex and dynamic role in life processes. They are believed to have oscillation modes of frequencies in the range of 1 to 1000 GHz. To measure such a high-frequency vibration, a linear laser cavity is designed to produce a train of femtosecond pulses of adjustable repetition rate. The method is then directly applied to liposomes, "artificial membrane", stained with a liphophilic potential sensitive dye. The spectral behavior of a selection of potential sensitive dyes in the membrane is also studied.
Date: December 1989
Creator: Jamasbi, Nooshin
Partner: UNT Libraries

Kinetics and Mechanisms of Ligand Exchange Reactions of Chelate Complexes

Description: Certain ligand substitution reactions proceed to a complete displacement of the chelate ligand. Certain reactions proceed through a mechanism involving an initial fission of the tungsten-sulfur bond to afford a coordinatively-unsaturated intermediate which is rapidly attacked by chlorobenzene. The resulting solvated intermediate establishes an equilibrium which involves desolvation-solvation. Although main group organometallic chemistry has received a great deal of attention, this discussion will be centered in organotransition metal chemistry, in particular, metal carbonyls.
Date: May 1989
Creator: Cortés, José E. (José Enrique)
Partner: UNT Libraries

Kinetics Studies of Substituted Tungsten Carbonyl Complexes

Description: Thermal reactions and flash photolysis are used to study the olefin bond-migration promoted by tungsten carbonyls. Substitution of piperidine (pip) by 2- allylphenyldiphenylphosphine (adpp) in the cis-(pip)(η^1- adpp)W(CO)-4 complex was investigated, and no olefin bond-migration was observed. This suggests that a vacant coordinated site adjacent to the coordinated olefin is an essential requirement for olefin bond rearrangement. The rates of olefin attack on the photogenerated coordinatively unsaturated species, cis-[(CB)(η^1-ol- P)W(CO)-4] (CB = chlorobenzene, p-ol = Ph-2P(CH-2)-3CH=CH-2; n = 1-4) were measured. Kinetics data obtained both in pure CB and in CB/cyclohexane mixtures support a dissociative mechanism in which the W-CB bond is broken in the transition state. In contrast to results observed in studies of other related systems, no olefin bond-migration is noted. This observation is attributed to P-W coordination at all stages of the reaction, which precludes formation of a reactive intermediate containing a vacant coordination site adjacent to a P-ol bond.
Date: August 1989
Creator: Wang, I-Hsiung, 1950-
Partner: UNT Libraries