Synthesis and coordination chemistry of functionalised and macrocyclic phosphines and arsines

Limon, Matthieu 2009. Synthesis and coordination chemistry of functionalised and macrocyclic phosphines and arsines. PhD Thesis, Cardiff University.

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Abstract

The results presented in this thesis are separated into three distinct sections. Chapter 2 describes the reaction of the manganese precursors Mn(OTf)(CO)3{o-C6H4(PH2)2}L 2.6, and Mn(OTf)(CO)3{C2H4(PH2)2} / 2.7, with a silver carbene transfer agent 1,3-dialtylbenzimidazol-2-ylidiene, 2.10, to give the new phosphido-phosphine manganese species 2.11 and 2.12. The resultant species 2.11 and 2.12 exist in two geometric forms, cis and trans, which have been characterised by X-Ray crystallography for 2.11. A new chiral rigid phospholane ligand 3(/)-hydroxy-phenylphospholane, 3.7, has been prepared from the reaction of phenylphosphine with enantiopure (/)-2-(oxiran-2-yl)ethyl-4-methylphenylsulfonate, 3.4. In order to enlarge the family of heterocyclic coordinated complexes, we herein report in Chapter 3 the synthesis of compounds Mo(k-PR s-3.7)2(CO)4, 3.16, Re(CO)5(k-PR,s-3.7), 3.17, Mn(OTf)(CO)4(k-PRfs-3.7), 3.18, Ru(cymene)a(k-PR,s-3.7), 3.19, FeCp'(CO)2(k-PR,s-3.7) PF6, 3.20, Rh(cod)CI(k-PR,s-3.7), 3.21, c/s-(k-PR,s-3.7)2PtCI2, 3.22, c/s-(k-PRfs-3.7)2PdCI2, 3.23. Finally, Chapter 4 presents the synthesis of new tribenzannulated dtarsine monophosphine macrocycle complexes prepared by a template method via dehydrofluorinative cyclisation of the di-ortfio-fluorophenylbisarsinobenzene ligand with PhPH2 at Mn(CO}3 + or Re(CO)3 + templates. The new macrocycles formed may expand the scientific understanding about phosphorus and arsenic chemistry. In order to enlarge this knowledge, other ways to introduce diarsenic ligands in our case 1,2-bis(arsino)benzene, 4.a, on a metal centre were attempted on MnBr(CO)5, 4.2, Mn(OTf)(CO)5, 4.3, Mn(CO)3(NCCH3)3 PF6, 4.4, Mn(CO)3(ace)3 PF6, 4.5, ReBr(CO)5, 4.6, Mn(OTf)(CO)5, 4.7, Cr(CO)3(NCCH3)3, 4.8, and Mo(CO)3(NCCH3)3, 4.9, precursors but no discrete complexes could be isolated and characterised.

Item Type:	Thesis (PhD)
Status:	Unpublished
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
ISBN:	9781303213793
Date of First Compliant Deposit:	30 March 2016
Last Modified:	12 Feb 2016 23:12
URI:	https://orca.cardiff.ac.uk/id/eprint/54767

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