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    Ionization-structure relationships in metal-phosphine interactions.

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    Author
    Jatcko, Mark Edward
    Issue Date
    1989
    Keywords
    Metal complexes
    Phosphine
    Photoelectron spectroscopy
    Electronic structure
    Advisor
    Litchenberger, Dennis L.
    
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    Show full item record
    Publisher
    The University of Arizona.
    Rights
    Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
    Abstract
    The techniques of valence photoelectron spectroscopy (PES), X-ray diffraction, molecular orbital calculations, and multi-nuclear NMR are combined in a comparison of metal-phosphine bonding in a series of phosphine substituted molybdenum and tungsten metal carbonyl complexes, M(CO)(6-n)(P)(n) [n = 1,2,3,4,6]. The phosphine, P, represents either the mono-dentate phosphine, PMe₃, or one phosphine unit in the diphosphines, Me₂P(CH₂)ₓPMe₂, [x = 1, bis(dimethylphosphino)methane (DMPM); x = 2, 1,2-bis(dimethylphosphino)ethane (DMPE)]. Comparison of PMe₃ and the diphosphines in mono-dentate coordination (i.e. η¹-Mo(CO)₅DMPE) indicates the σ-donor strength is essentially identical for the three phosphines studied. Comparison of PMe₃ and the diphosphines in cis-chelating geometries reveals essentially identical charge at the coordinated phosphorus atoms and nearly identical charge at the metal center for cis-M(CO)₄(PMe₃)₂ and cis-M(CO)₄DMPE despite different local P-M-P bond angles. The X-ray crystal structures reveal a "twist" of the phosphine ligand when in sterically strained coordination geometries. The phosphine twist results in a "bent" metal-phosphine bond and is evaluated based on both electronic and steric considerations. The phosphine twist principle is used in studies on the nature of phosphine ligand electronic effects in the M(CO)(6-n)(P)(n) series at high substitution numbers, n. The PES data of the DMPE complexes for n = 4, cis-Mo(CO)₂(DMPE)₂, and n = 6, Mo(DMPE)₃, show symmetric metal electronic structure, but also a deviation from the previously observed additive behavior of phosphine electronic effects. The PES data for cis-Mo(CO)₂(PMe₃)₄ reveal a symmetric metal electronic structure due to sterically induced ligand-ligand interactions in this metal carbonyl complex. Multi-nuclear NMR data (³¹P and ⁹⁵Mo) are presented and the results discussed in light of the important ligand-ligand interactions observed in the PES studies. In addition, comparison of the NMR results for the mono-dentate and chelating phosphine complexes and the PES metal electronic structures provides a possible contribution to the ring chelate effect that is observed in the ³¹P and ⁹⁵Mo chemical shifts. The ring chelate effect refers to the unexplained relative differences between the ³¹P and ⁹⁵Mo chemical shifts of the cis-(PR₃)₂ complexes and the chelating diphosphine analogues.
    Type
    text
    Dissertation-Reproduction (electronic)
    Degree Name
    Ph.D.
    Degree Level
    doctoral
    Degree Program
    Chemistry
    Graduate College
    Degree Grantor
    University of Arizona
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    Dissertations

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