Utilisation of halophosphine and aminophosphine ligands in organoruthenium chemistry

This thesis concerns the syntheses and reactivity of areneruthenium complexescontaining halophosphine and aminophosphine ligands. Methylcyclopentadienylrutheniumchemistry is also developed together with corresponding tertbutylcyclopentadienylrutheniumchemistry. All the new compounds prepared arepseudo-octahedral with the arene or cyclopentadienyl ligand being facially coordinated.The first chapter contains a literature review of the chemistry of the rutheniumcomplex [RuCl 2(r| 6 -/?-cymene)] 2 , which is one of our starting materials. The chemistryof the ligands tris(dimethylamino)phosphine, trifluorophosphine, trichlorophosphine,tribromophosphine, dimethylaminodifluorophosphine and tert-butyldichlorophosphineis 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 bymultinuclear N.M.R spectroscopy; x-ray crystallographic structure determinations werecarried 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 oftrifluorophosphine gas on a small scale is described. The observation of halogen exchange between the ruthenium centre and halophosphines is reported and the trendsin '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 newalkylcyclopentadienyl 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 havebeen produced from these precursors. The chapter ends with a spectroscopiccomparison of alkylcyclopentadienylruthenium derivatives.The fifth chapter contains all the experimental work carried out for chapters two,three, and fourThe sixth chapter contains suggestions for future workThe appendices contain the x-ray crystallographic metric data for nine newcompounds: [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