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Title: Syntheses and rearrangement reactions of some tertiary phosphine complexes of ruthenium
Author: Armit, Peter W.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1977
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Chapter 1: The basic principle of nmr are described and some of the techniques and applications of 31P nmr are given. 31P chemical shifts for monotertiaryphosphine coordination compounds are tabulated. Chapter 2: After a brief survey of monotertiary phosphine complexes of ruthenium, the preparation of the compounds RuX2L3(L = PEtPh2), RuX2L4(L = PMePh2, Me2Ph) and Ru2X4L5(L = PC1Ph2, PEt2Ph) by the reaction of tertiaryphosphine with RuX2(PPh3)3 or 4 (X = C1,Br) in hexane or light petroleum is reported. The structures and rearrangement reactions of these compounds in polar and non-polar media are examined chiefly by means of 31P nmr spectroscopy and possible mechanisms for the rearrangements are discussed. In non-polar solvents RuCl2(PPh3)3 loses a PPh3 group whereas in highly polar solvents dissociation of a chloride ligand occurs. RuCl2(PEtPh2)3 rearranges to [Ru2C13(PEtPh2)6]Cl in polar solvents and to Ru2C14(PEtPh2)5 in non-polar solvents. RuCl2(PMePh2)4 rearranges in solution to form Ru2Cl4(PMePh2)5 and [Ru2Cl3(PMePh2)6]Cl. cis-RuC12(PMe2Ph)4 readily rearranges to [Ru2Cl3(PMe2Ph)6]Cl. Chapter 3: The preparations of the complexes Ru2Cl4(CS)2(PPh3)4 and Ru2Cl4CS(PPh3)4 are given. A mechanism involving the 5 co-ordinate intermediate "RuC12CS(PPh3)2" is invoked to explain their formation and also that of Ru2Cl4(CS)2(PPh3)3 from Ru2Cl4(CS)2(PPh3)4. RuZCl5CS(PPh3)3 is formed from Ru2C14CS(PPh3)4 by intermolecular displacement of PPh3 by Cl. Chapter 4: RUM2CO(PPh3)2dmf dissolves in non-polar solvents to form the five coordinate "RuC12CO(PPh3)2". This is used to verify the rearrangement mechanism proposed in chapter 3 by synthesising the corresponding carbonyl complexes Ru2Cl4(CO)2(PPh3)3 and Ru2C14CO(PPh3)4. In polar solvents [Ru2C13(CO)2(PPh3)4]+ is formed. 31P nmr is used to study these reactions. Equimolar quantities of RuCl2CO(PPh3)Zdmfand RuBr2(PPh3)3 (or RuBr2CO(PPh3)2dmf and RuC12(PPh3)3) react to form Ru2Br2Cl2CO(PPh3)4. Chapter 5: RuCl2CO(PEtPh2)3dmf is prepared as the corresponding PPh3 complex. It rearranges in a similar manner and although the products may not be obtained in pure form they may be identified by 31P nmr. [Ru2C1ACcJPEtPh2)4]+ forms more readily than its PPh3 analogue. RuC12CO(PEtPh2)3 is also formed as a major product in these reactions.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available