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20220104090738.0 |
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880317s1986 xx a bm 000 0 eng d |
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|9 AAA3320AM
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|a (OCoLC)17640462
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|a (OCoLC)ocm17640462
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|a TXA
|b eng
|c TXA
|d OCLCQ
|d OCLCF
|d OCLCO
|d OCLCQ
|d OCLCA
|d TXA
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| 049 |
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|a TXAM
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| 099 |
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|a 1986
|a Dissertation
|a T671
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| 100 |
1 |
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|a Tooley, Patricia Ann.
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| 245 |
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|a Catalytic and mechanistic studies of some anionic transition metal carbonyl hydrides.
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| 264 |
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|c 1986.
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| 300 |
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|a xiii, 149 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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| 500 |
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|a Vita.
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| 502 |
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|b Ph. D. in Chemistry
|c Texas A & M University
|d 1986
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| 504 |
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|a Includes bibliographical references (leaves 137-148).
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| 520 |
3 |
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|a As PPN⁺ (bistriphenylphosphineimminium) salts the anionic metal hydrides HFeM(CO)₉⁻ (M = Cr, Mo, W) were shown to be olefin isomerization catalysts under mild conditions (25°C, fluorescent lighting) toward the conversion of allylbenzene to the cis- and trans-propenylbenzenes and 1-hexene to internal olefins. The use of DFeM(CO)₉⁻ as an olefin isomerization catalyst was found to lead to the incorporation of d-label into the olefinic products. The activity of HFe(CO)₄⁻ was examined in the presence of alkali metal ions (Li⁺ or Na⁺) as well as in the presence of hydride abstracting agents (Ph₃C⁺ or BF₃). Evidence presented suggests the role of M(CO)₅⁰ to be similar to the alkali cations in promoting CO labilization and thus promoting catalysis on the Fe-H⁻ center. The reaction of H₂ with species of the type BM(CO)₅⁻ (B = Bronsted base; M = Cr, Mo, W) was shown to lead to the formal products of heterolytic cleavage, HB and HM(CO)₅⁻. For B = OAc⁻ or HM(CO)₅⁻, the catalytic hydrogenation of aldehydes, ketones, and α,β-unsaturated ketones was carried out. Mechanistic models consistent with observations made using in situ high pressure FTIR and isotopic labelling studies include (1) ligand assisted heterolytic activation of H₂, and (2) an alkoxide stabilized oxidative addition (dihydride) product or a base stabilized η²-H₂-metal carbonyl intermediate. Subsequent steps involve hydride attack on the carbonyl carbon followed by protonation to produce the alcohol product. For M(CO)₅R⁻, with B formally equal to R⁻ (R = Me, Ph, Bzl), products of simple elimination (or R⁻/H⁻) exchange), RH and HM(CO)₅⁻, were observed for M = W with activities Me > Ph >> Bzl. For M = Cr, carbonyl insertion products, i.e., aldehydes and alcohols were observed. Comparison studies were performed on the anionic iron alkyls, RFe(CO)₄⁻ (R = Me, Bzl). Like the W alkyls, products were those of simple elimination, RH and HFe(CO)₄⁻. A mechanistic model consistent with observed results involves the intermediacy of a molecular H₂ complex for the group 6 complexes. For the iron alkyls, the oxidative addition product RFe(H)₂(CO)₃⁻ is assumed to be an intermediate. For the heterobimetallic system RFeW(CO)₉⁻, with B = RFe(CO)₄⁻ (R = H, Me), products formed were HFe(CO)₄⁻, W(CO)₆, μ-HW₂(CO)₁₀⁻, and HFe₃(CO)₁₁⁻. Mechanisms proposed include (1) CO labilization of the heterobimetallic system followed by oxidative addition of H₂ on the Fe center, and (2) heterolytic activation of dihydrogen between the metal centers.
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| 650 |
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|a Organometallic compounds.
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| 650 |
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|a Transition metal catalysts.
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| 650 |
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4 |
|a Major chemistry.
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| 655 |
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7 |
|a Academic theses
|2 lcgft
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| 700 |
1 |
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|a Akgerman, Aydin,
|e degree committee member.
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| 700 |
1 |
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|a Darensbourg, Donald J.,
|e degree committee member.
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| 700 |
1 |
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|a Darensbourg, Marcetta Y.,
|e degree supervisor.
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| 700 |
1 |
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|a Fackler, J. P.,
|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 |
|u http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=752634331&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD
|z Link to ProQuest copy
|t 0
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| 856 |
4 |
1 |
|u https://hdl.handle.net/1969.1/DISSERTATIONS-17162
|z Link to OAKTrust copy
|t 0
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| 994 |
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|a C0
|b TXA
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| 999 |
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|s 8ef5b740-a69d-3bf1-8269-b8cd6c64b17c
|i 2d7fe97d-7c91-3ab5-ad5b-831d5a110830
|t 0
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| 952 |
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|p noncirc
|a Texas A&M University
|b J.J. Pickle Campus
|c High Density Repository
|s HDR
|d Remote Storage
|t 0
|e 1986 Dissertation T671
|h Other scheme
|i unmediated -- volume
|m A14839615423
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| 952 |
f |
f |
|a Texas A&M University
|b College Station
|c Electronic Resources
|s www_evans
|d Available Online
|t 0
|e 1986 Dissertation T671
|h Other scheme
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| 998 |
f |
f |
|a 1986 Dissertation T671
|t 0
|l Remote Storage
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| 998 |
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|a 1986 Dissertation T671
|t 0
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