Utilisation of halophosphine and aminophosphine ligands in organoruthenium chemistry

Boshaala, AMA 2008, Utilisation of halophosphine and aminophosphine ligands in organoruthenium chemistry , PhD thesis, University of Salford.

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Abstract

This thesis concerns the syntheses and reactivity of areneruthenium complexes containing halophosphine and aminophosphine ligands. Methylcyclopentadienylruthenium chemistry is also developed together with corresponding tertbutylcyclopentadienylruthenium chemistry. All the new compounds prepared are pseudo-octahedral with the arene or cyclopentadienyl ligand being facially coordinated. The first chapter contains a literature review of the chemistry of the ruthenium complex [RuCl 2(r| 6 -/?-cymene)] 2 , which is one of our starting materials. The chemistry of the ligands tris(dimethylamino)phosphine, trifluorophosphine, trichlorophosphine, tribromophosphine, dimethylaminodifluorophosphine and tert-butyldichlorophosphine is also detailed. The second chapter reports the syntheses and reactivity of the neutral compounds [RuX 2 (r| 6-/>cymene)P(NMe 2 ) 3 ] (X= Cl, Br, and I) and the cationic tris- (dimethylamino)phosphine complexes [RuCl(r| 6 -/?-cymene)P(NMe2 ) 3 (L)] (L = CO, CN'Bu, PPh3 , P(OPh3 ) 3 , P(OCH 3 ) 3 SMe 2 ). The new complexes were characterized by multinuclear N.M.R spectroscopy; x-ray crystallographic structure determinations were carried out on [RuCl2 (r) 6-/?-cymene)P(NMe 2 ) 3 ], [RuI 2 (r| 6 -/>-cymene)P(NMe 2 ) 3 ], [RuCl(nVcymene)P(NMe2 ) 3 (CO)]PF 6 , [RuCl(Ti 6 -p-cymene)P(NMe 2 ) 3 S(CH 3 ) 2 ]PF 6 . and [RuCl 2 (n 6 -/7-cymene)(HNMe 2 )]. The third chapter describes the syntheses and reactivity of [RuX 2 (r| 6 -pcymene) P(Z) 3 ] (X= Cl, Br, and I, Z = Cl, Br. and F). The generation of trifluorophosphine gas on a small scale is described. The observation of halogen exchange between the ruthenium centre and halophosphines is reported and the trends in 'j(P-F) are described in the two series [RuX 2 (n 6-/>cymene)(PF 3 )] and [RuX 2 (n 6 -/?- cymene)(PF 2 {NMe 2 })]. The fourth chapter contains the syntheses of two series of new alkylcyclopentadienyl complexes [(r| 5 -tert-BuCp)Ru(PPh3 )(L)Cl] and [(ry- MeCp)Ru(PPh3 )(L)Cl], (L = CO, CN'Bu, PPh 3 ) and [[(r| 5 -ter/-BuCp)Ru((L') 2 Cl] (L 1 = P(OPh 3 ) 3 , P(OCH 3 ) 3 , PPh3 , and dppm). Some hydride and cationic complexes have been produced from these precursors. The chapter ends with a spectroscopic comparison of alkylcyclopentadienylruthenium derivatives. The fifth chapter contains all the experimental work carried out for chapters two, three, and four The sixth chapter contains suggestions for future work The appendices contain the x-ray crystallographic metric data for nine new compounds: [RuCl 2 (n 6 -p-cymene)P(NMe 2 ) 3 J, [RuI 2 (n 6 -p-cymene)P(NMe2 ) 3 J, [RuCl(n 6 - /7-cymene)P(NMe 2 ) 3 (CO)]PF 6 , [RuCl(r| 6 -/7-cymene)P(NMe 2 )3 S(CH 3 ) 2 ]PF 6 , [RuCl 2 (n 6 - p-cymene)(HNMe 2 )], [RuCl 2 (r| 6 -p-cymene)PF 3 ], [RuCl 2 (n 6 -p-cymene)PF 2 (NMe 2 )], [(r| 5 -tert-BuCp)Ru(PPh 3 )2 (CN t Bu)]BF4 , and[[(Ti 5 -MeCp)Ru(dppf)P(OCH 3 ) 3 ]BF4 .

Item Type: Thesis (PhD)
Contributors: Simpson, SJ (Supervisor)
Schools: Schools > School of Computing, Science and Engineering
Depositing User: Institutional Repository
Date Deposited: 16 Aug 2021 14:01
Last Modified: 27 Aug 2021 21:57
URI: http://usir.salford.ac.uk/id/eprint/61572

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