The first of the two novel bidentate, fluorinated diphosphine ligands was successfully synthesised via the low temperature reaction of HFC-134a with LDA followed by the addition of the chlorinated phosphine species, 1,2-bis(dichlorophosphino)ethane. The second of these ligands required the further addition of n-BuLi to the synthesised ligand 1, [(F2C=CF)2PCH2CH2P(FC=CF2)2] to yield [(BuFC=CF)2)PCH2CH2P(FC=CFBu)2] (2). Both of these ligands were produced in satisfactory yields and analysis was completed through the study of the obtained 1H NMR, 19F NMR and 31P {1H} NMR spectra. These two phosphine species were reacted further through the addition H2O2 to yield the P (V) oxide phosphine analogues. The other P (V) compounds produced were the corresponding selenide species of both ligands, formed after refluxing a solution of either ligand with an excess of elemental selenium, and the difluoride species of the first ligand, formed following the addition of multiple crystals of XeF2. As phosphine species such as these typically find the greatest use as ligands to transition metals, complexes of these ligands bonded to Mo, Pt and Pd were also synthesised. The ν(CO) stretching frequency, seen in the IR data for the Mo carbonyl complexes of both ligands, was used as one method by which the electronic properties of the ligands were measured. The other method invovled measuring the 1J coupling constants, measured in Hertz, of the Pt satellites, seen in the 31P NMR spectra for the two synthesised Pt complexes. It is through comparing these collected values and comparing them to known data that the relative electron donating power of these two fluorinated phosphines has been measured.
Date of Award | 1 Aug 2020 |
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Original language | English |
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Awarding Institution | - The University of Manchester
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Supervisor | Alan Brisdon (Supervisor) & Louise Natrajan (Supervisor) |
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Synthesis and Coordination Chemistry of Bidentate Fluorovinyl Phosphine Ligands
Mccormack, R. (Author). 1 Aug 2020
Student thesis: Master of Science by Research