Utilisation of halophosphine and aminophosphine ligands in organoruthenium chemistry

Boshaala, AMA

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 .

• Thesis Type: Thesis
• Deposit Date: Aug 16, 2021
• Award Date: Mar 1, 2008