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Activation of white phosphorus by molybdenum- and uranium tris-amides

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dc.contributor.advisor Christopher C. Cummins. en_US Stephens, Frances H. (Frances Helen), 1977- en_US
dc.contributor.other Massachusetts Institute of Technology. Dept. of Chemistry. en_US 2005-06-02T18:53:06Z 2005-06-02T18:53:06Z 2004 en_US 2004 en_US
dc.description Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004. en_US
dc.description Vita. en_US
dc.description Includes bibliographical references. en_US
dc.description.abstract Molybdaziridine-hydride Mo(H)([eta]²-Me₂C=NAr)(N[i-Pr]Ar)₂ (1, Ar = 3,5-C₆H₃Me₂) acts as a source of its three-coordinate isomer Mo(N[i-Pr]Ar)₃ (2). This relationship has been probed via an investigation of the coordination chemistry of 1 and Mo(N[t-Bu]Ar)3 (3), a bulky analog of 2, with isocyanides RNC (R = 1-adamantyl, tert-butyl) and white phosphorus (P₄). A comparison of the rates and activation parameters of these reactions indicates that 2 is not an intermediate on the pathway from 1 to products, but rather than the molybdaziridine-hydride "opens" upon substrate binding in an associative process. Synthesis and characterization of 1:1 and 1:2 isocyanide adducts of 2 and 3, and bridging and terminal Pn compounds of molybdenum derived from the element P4 and their alcoholysis products are presented. The uranium tris-amide compounds (THF)U(N[R]Ar)₃ (R = t-Bu, 1-Ad) reacted with white phosphorus. The unique products contain a square tetraphosphorus moiety characterized formally as the dianion P₄â–¡â–¡₂â‚‹. Structural and theoretical analyses are provided for this system. en_US
dc.description.statementofresponsibility by Frances H. Stephens. en_US
dc.format.extent 201, [2] p. en_US
dc.format.extent 12551861 bytes
dc.format.extent 12576587 bytes
dc.format.mimetype application/pdf
dc.format.mimetype application/pdf
dc.language.iso eng en_US
dc.publisher Massachusetts Institute of Technology en_US
dc.rights M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. en_US
dc.subject Chemistry. en_US
dc.title Activation of white phosphorus by molybdenum- and uranium tris-amides en_US
dc.type Thesis en_US Ph.D. en_US
dc.contributor.department Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.identifier.oclc 56571129 en_US

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