THE SYNTHESIS, CHARACTERIZATION, AND REACTIONS OF DIPHOSPHINE MONOXIDE COMPLEXES OF SELECTED TRANSITION METALS

<p>The synthesis, characterization and reactions of transition metal complexes containing diphosphine oxide, R(,2)P-P(O)PR(,2), and diphosphoxane, R(,2)P-O-PR(,2), ligands have been studied. The diphosphoxane tautomer, which is unstable in the free state has been observed to be stabilized by coordination to Mo(O) and Cu(I).</p><p>The reactivity of cis-(CO)(,4)Mo(R(,2)P-O-PR(,2)) (R = Ph, ptolyl) towards halogen-oxidation has been studied. The new seven-coordinate complexes (CO)(,3)Mo(R(,2)P-O-PR(,2))X(,2) (R = Ph, X = I; R = p-tolyl, X = Br), as well as the known (CO)(,3)Mo(Ph(,2)PCH(,2)PPh(,2))I(,2) have been observed to exhibit temperature dependent ('31)P NMR consistent with rapid topological isomerization and intramolecular rearrangement of a given isomer.</p><p>The reaction of coordinated aminophosphines has been shown to lead, via fluoride exchange, to mixed fluorophospine-aminophosphine complexes. This result is in agreement with published reports of fluoride exchange reactions which occur via initial coordination of BF(,3) etherate to the nitrogen donor of free aminophosphines.</p><p>The reaction of Ph(,2)P-P(O)Ph(,2) with cp(CO)(,2)FeTHF BF(,4) has resulted in a redistribution reaction leading to cp(CO)(,2)FePh(,2)P-PPh(,2)Fe(CO)(,2)cp BF(,4) (,2). A mechanism for this unusual transformation has been proposed based on(, )('31)P NMR evidence.</p><p>Five new complexes, cis-(CO)(,4)Mo(Ph(,2)P-O-PPh(,2)),cis-(CO)(,4)Mo(Ph(,2)P-O-P(O) (Ph)PPh(,2)), trans-(CO)(,4)Mo Ph(,2)P-P(O) (OEt)(,2)) (,2), (CO)(,3)Mo(Ph(,2)P-O-PPh(,2))I(,2), and (CuCl)(,2)Ph(,2)P-O-PPh(,2) (,2) have been structurally characterized by x-ray crystallography. ('31)P NMR and IR spectroscopy have been used extensively throughout the research described in this dissertation and the results of these spectroscopic investigations have been discussed.</p><p>Note: In this dissertation a convention will be used to simplify the drawing of metal carbonyl complexes. In this convention a.</p><p>will be used to represent a metal carbonyl. The above drawing is a representation of Mo(CO)(,6) in which the octahedral arrangement of the six carbon monoxide groups is shown simply as six lines radiating from the metal center. Substitution of carbon monoxide by a phosphine will be explicitly shown, ie.,</p><p>is a drawing of the complex trans-(CO)(,4)Mo(Ph(,2)PCl)(,2).</p>

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Dissertation

Year

1984

Author dc:creator

• BRADLEY, FONTAINE COSBY

• Chemistry
• Inorganic

Repository record dc:identifier

https://scholars.unh.edu/dissertation/1439

OAI identifier oai:identifier

oai:scholars.unh.edu:dissertation-2438