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| 008 |
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| 035 |
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|a (OCoLC)ocm26820904
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| 035 |
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|9 AFU7036AM
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| 040 |
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|a TXA
|b eng
|c TXA
|d OCLCQ
|d OCLCO
|d OCLCQ
|d OCLCA
|d TXA
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| 035 |
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|a (OCoLC)26820904
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| 049 |
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|a TXAM
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| 099 |
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|a 1991
|a Dissertation
|a B621
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| 100 |
1 |
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|a Bischoff, Christopher John,
|d 1964-
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| 245 |
1 |
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|a Structural and kinetic investigations of group VI and group VIII metal carbonyl derivatives containing trisodium tris-m-sulfonatophenyl phosphine ligands /
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| 264 |
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|c 1991.
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| 300 |
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|a xviii, 154 leaves :
|b illustrations ;
|c 29 cm
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| 336 |
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|a text
|b txt
|2 rdacontent
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| 337 |
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|a unmediated
|b n
|2 rdamedia
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| 338 |
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|a volume
|b nc
|2 rdacarrier
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| 500 |
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|a Typescript (photocopy).
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| 502 |
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|b Ph. D.
|c Texas A & M University
|d 1991
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| 500 |
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|a Vita.
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| 504 |
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|a Includes bibliographical references.
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| 500 |
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|a "Major subject: Chemistry."
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| 650 |
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0 |
|a Organometallic compounds
|x Structure.
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| 650 |
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0 |
|a Organometallic compounds
|x Reactivity.
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| 650 |
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0 |
|a Ligands.
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| 650 |
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0 |
|a Catalysis.
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| 650 |
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4 |
|a Major chemistry.
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| 655 |
|
7 |
|a Academic theses
|2 lcgft
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| 700 |
1 |
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|a Darensbourg, Donald J.,
|e degree supervisor.
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| 700 |
1 |
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|a Anthony, R. G.,
|e degree committee member.
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| 700 |
1 |
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|a Lunsford, J.,
|e degree committee member.
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| 700 |
1 |
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|a Zingaro, R.,
|e degree committee member.
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| 710 |
2 |
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|a Texas A & M University,
|e degree granting institution.
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| 856 |
4 |
1 |
|x http://hdl.handle.net/1969.1/DISSERTATIONS-1274337
|z Link to OAKTrust copy
|t 0
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| 520 |
3 |
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|6 520-00
|a Several group 6 carbonyl derivatives containing the trisodium tris-m-sulfanatophenyl phosphine (TPPTS) ligand have been synthesized as part of a kinetic investigation into the possible intramolecular interactions of these ligands. Kinetic studies into the dissociation of both the water-soluble, TPPTS ligand and its organic-soluble analog, PPh3, from M(CO)5L (M = Mo, W) complexes have been followed by in situ internal reflectance infrared spectroscopy. Kinetic measurements taken in water, THF, and mixtures of THF:H2O show the loss of phosphine to follow a first-order dependence on the metal substrate and zero order dependence on the incoming ligand (CO). Activation parameters determined for both Mo(CO)5TPPTS and W(CO)5TPPTS in 1:1 THF:H2O are ΔH[double dagger]= 28.0[plus or minus]1.3 and ΔS[double dagger]= -4.80[plus or minus]3.33, ΔH[double dagger]= 31.1[plus or minus]1.4 and ΔS[double dagger]= -1.20[plus or minus]3.4 kcal mol^-1 and eu, respectively. These values are compared to their analogous Mo(CO)5PPh3 and W(CO)5PPh3 activation parameters, showing only slight differences. A series of kinetics for the loss of a phosphine from cis-Mo(CO)4L2 complexes were carried out in 2-methoxyethanol under an atmosphere of CO and at temperatures between 50 to 80 °C. The activation parameters for the reaction of carbon monoxide with cis-Mo(CO)4[TPPTS]2, cis-Mo(CO)4[PPh3]2, and [Na-Kryptofix-221]6[cis-Mo(CO)4{P(m-C6H4SO3)3}2] were determined to be ΔH[double dagger]= 28.9[plus or minus]2.2 and ΔS[double dagger]= 12.2[plus or minus]6.7, ΔH[double dagger]= 28.8[plus or minus]0.34 and ΔS[double dagger]= 12.5[plus or minus]1.0, and ΔH[double dagger]= 26.3[plus or minus]1.8 and ΔS[double dagger]= 8.7[plus or minus]5.5 kcal mol^-1 and eu, respectively. Results of this study indicate a slight interaction between neighboring TPPTS ligands. Under similar conditions cis-W(CO)4L2 (L = TPPTS and PPh3) complexes were found to undergo exclusively intramolecular rearrangements to the corresponding trans species. This intramolecular rearrangement for both cis-W(CO)4 (TPPTS)2 and cis-W(CO)4[TPPTS]2 and cis-W(CO)4[PPh3]2 was determined to be a lower energy pathway than phosphine dissociation with activation numbers of ΔH[double dagger]= 19.0[plus or minus]3.9 and ΔS[double dagger]= -18.4[plus or minus]11.7 and ΔH[double dagger]= 17.7[plus or minus]1.2 and ΔS[double dagger]= -21.5[plus or minus]3.8 kcal mol^-1 and eu, respectively...
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| 856 |
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|u http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=746243571&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD
|z Link to OAKTrust copy
|t 0
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| 994 |
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|a Texas A&M University
|b J.J. Pickle Campus
|c High Density Repository
|s HDR
|d Remote Storage
|t 0
|e 1991 Dissertation B621
|h Other scheme
|i unmediated -- volume
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|a Texas A&M University
|b College Station
|c Electronic Resources
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|d Available Online
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|e 1991 Dissertation B621
|h Other scheme
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|a 1991 Dissertation B621
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| 998 |
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|a 1991 Dissertation B621
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