2026-09-18T22:48:39Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/178412022-01-13T07:54:21Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Christopher C. Cummins.
Stephens, Frances H. (Frances Helen), 1977-
Massachusetts Institute of Technology. Dept. of Chemistry.
Massachusetts Institute of Technology. Department of Chemistry
2005-06-02T18:53:06Z
2005-06-02T18:53:06Z
2004
2004
http://hdl.handle.net/1721.1/17841
56571129
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004.
Vita.
Includes bibliographical references.
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.
by Frances H. Stephens.
Ph.D.
201, [2] p.
12551861 bytes
12576587 bytes
application/pdf
application/pdf
eng
Massachusetts Institute of Technology
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http://dspace.mit.edu/handle/1721.1/7582
Chemistry.
Activation of white phosphorus by molybdenum- and uranium tris-amides
Thesis
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Publication
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<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.</Abstract>
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