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Title: Advances in polyaromatic and ferrocenyl phosphine chemistry
Author: Lake, Andrew J.
Awarding Body: Loughborough University
Current Institution: Loughborough University
Date of Award: 2010
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Condensation of Ph2PCH2OH with a range of polyaromatic substituted secondary amines afforded a new set of 'hybrid' phosphine ligands of the type {RCH2N(CH2PPh2)CH2}2 and RCH2N(CH2PPh2)CH2CH3 (R = various planar aromatic groups). The coordination chemistry of these new mono and bidentate ligands towards a range of transition metal centres including Mo(0), Au(I), Rh(I), Ni(II), Pd(II), Pt(II) and Ru(II) was investigated. Ditertiary phosphines of the form {RCH2N(CH2PPh2)CH2}2 were found to be capable of bridging two transition metal centres in addition to forming rare examples of nine-membered cis- and trans- chelate complexes. Single crystal X-ray analysis of these coordination compounds revealed several types of inter- and intramolecular packing interactions (including a C-H···Pt interaction and slipped intermolecular π····π stacking), and also confirmed the rare trans-diphosphine coordination mode. Fluorescent emission measurements have been undertaken on these new tertiary phosphines and their coordination compounds, and these luminescent properties are discussed. A preliminary investigation into the chemosensory behaviour of selected compounds has been undertaken. Using RPCH2OH (RP = Ph2P, Cy2P or AdP = 1,3,5,7,-tetramethyl-2,4,8-trioxa-6- phosphaadamantane) as a versatile precursor, a range of ferrocenyl (Fc) tertiary phosphines have been prepared from a selection of primary and secondary amines. The coordination chemistry of these new mono and bidentate ligands towards several transition metal centres including Cr(0), Mo(0), Au(I), Rh(I), Ru(II), Pd(II) and Pt(II) was investigated. In particular, the previous chemistry was expanded to prepare several new diferrocenyl phosphines of the form {FcCH2N(CH2PR)CH2}2. In a similar manner to their polyaromatic counterparts, these ditertiary phosphines were found to be capable of coordination through both bridging and cis- / trans-chelating modes. Notably, single crystal X-ray analysis was used to confirm the formation of an extremely rare example of a dimeric trans, trans-[Rh(CO)Cl{phosphine}2]2 complex; thought to be the first crystallographically characterised metallacycle containing an Rh2Fe4 arrangement of metal centres. In addition to this {FcCH2N(CH2PR)CH2}2 chemistry, a rare example of a triferrocenyl ditertiary ii phosphine, {FcCH2N(CH2PPh2)CH2}2Fc, was prepared, as well as a macrocyclic ditertiary ferrocenyl phosphine, C10H8Fe(CH2N(CH2PPh2)CH2)2CH2. The coordination chemistry of {FcCH2N(CH2PPh2)CH2}2Fc led to the formation of two unusual examples of pentametallic diphosphine coordination complexes with a Fe3Au2 and Fe3Ru2 arrangement of metal centres. The development of a new phosphinoamine, (Ph2P)2NCH2Fc, and a new ferrocenyl iminophosphine, Ph2PCH(Ph)CH2C(H)NCH2Fc, are also discussed, in addition to a brief investigation of their coordination chemistry. Electrochemical measurements have also been undertaken on these ferrocenyl ligands and their respective coordination compounds (when purity, yield and stability would allow), and their redox chemistry discussed. A series of novel phosphorus(III) containing ligands of the forms (R)N(CH2PPh2)2 and (R)NHCOCH2N(CH2PPh2)2 (R = functionalised planar aromatic or ferrocenyl group) have been prepared. The phosphines were found to readily coordinate several transition metals including Pt(II), Pd(II) and Ru(II) to form a series of new cis- chelate and bridged bimetallic complexes. Analysis by single crystal X-ray diffraction revealed several types of inter- and intramolecular hydrogen bonding within the molecular structures of the phosphines and their coordination compounds, including the formation of several intermolecular 1D chains and the presence of an intramolecular N-H···N bond, which forces a 'scorpion-like' conformation.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Tertiary phosphine ; Mannich based condensation ; Ferrocenyl compounds ; Coordination chemistry ; Late-transition metals ; Trans-spanning diphosphines ; X-ray crystallography ; Electrochemical studies ; Luminescent studies ; Chemosensors