Synthesis, structure and reactivity of chiral cyclopentadienylruthenium(II) complexes

This thesis concerns the preparation, structural, and reactivity studies of newchiral monometallic cyclopentadienylruthenium(n) complexes exhibiting a combinationof metal-centred and ligand-derived chirality.The introductory chapter provides an overview of the types of chiralorganometallic complexes previously reported, general methods of synthesis,separation, and techniques for stereochemical determination.In the second chapter, a range of chiral cyclopentadienylruthenium(n) aminecomplexes {[(Ti 5 -C 5 H5)Ru(PPh3 )(L)(NHRR')]PF6 (L = CN*Bu, CO)}, prepared fromtheir precursor halides ((±)-[(rj 5 -C 5 H5)Ru(PPh 3 )(L)X], X = Cl or I) via treatment withvarious amines (1°: cyclohexylamine, S(-)-a-methylbenzylamine, /?(-)-1-cyclohexylethylamine,(±)-l-(l-naphthyl)ethylamine; 2°: diethylamine, 5(-)-A^-methyl-l-phenylethylamine)in the presence of a halide abstractor are described. Various reactions anddecomplexations are discussed.The third chapter contains the synthesis and reactions of sulphur donorcomplexes (dimethyl sulphoxide, (±)-2-methyl-l-butanethiol) which are preparedanalogously. An X-ray crystal structure determined for (±)-[(rj 5 -C 5 H5)Ru(PPh 3 )-(CNtBu)(Me 2 SO)]PF6 is also discussed.The fourth chapter describes the preparation of the chiral ligand S(-)-oc-methylbenzylisonitrileby Phase-Transfer Hoffmann Isocarbylamine reaction. Complexes(^^c,^5c)-[(Ti 5 -C5H 5 )Ru(PPh 3 )(CNCHMePh)Cl] and (RRu Sc3Ru Sc )-[(T} 5 -C 5 H 5 )Ru-(PPh 3 )(CNt Bu)(CNCHMePh)(NH 3 )]PF6 , which were subsequently prepared by knownprocedures, and the X-ray crystal structure determined for the latter complex is alsopresented.Alkoxycarbene complexes (±)-[(Ti 5 -C 5 H5)Ru(PPh 3 )(CNtBu)(L)]PF6 (L =C{OMe}CH2 Ph, C{CH 2 } 3 O) are presented in the fifth chapter. Methylation of thealkoxylvinyl or metallated carbene derivatives with iodomethane are discussed for theacyclic and cyclic systems respectively.The sixth chapter contains attempted reactions of the halide precursor and of themolecular dihydrogen complex (±)-[(r| 5 -C 5 H 5 )Ru(PPh 3 )(CNt Bu)(Ti 2 -H2)]PF6 (e.g.,haloalkane, aldehydes, ketones, alkene).Complexes containing an asymmetrically disubstituted rc-bonded ligand, TJ -1-ethyl-3-methylcyclopentadiene which induces planar chirality, e.g., [(r| 5 -l-Et-3-Me-C 5 H 3 )Ru(PPh3 )(L)Cl] (L - PPh 3 , CN'Bu, CO, P(OMe) 3 ) and l(r| 5 -l-Et-3-Me-C 5 H3 )Ru-(PPh3 )(L)(NH 2 CHMePh)]PF6 (L = CN'Bu, P(OMe) 3 ) are described in the seventhchapter.Spontaneous resolution by crystallisation are reported as assayed from X-raycrystal structures determined for single crystals (i.e., (5««)-[(r| 5 -C5H5)Ru(PPh3 )-(CNtBu)(NH2Cy)]PF6 and (RpiSRuScH(r( 5 - l-Et-3-Me-C 5 H 3 )Ru(PPh3 )(CNtBu)(NH2 CHMePh)]PF6). These are discussed in chapters 2 and 7 respectively.The eighth chapter contain the experimental details for chapters 2 to 7.

Level dc:type.qualificationlevel

Doctoral (Level 8)

Year dc:date.issued

1996

Author dc:creator

• Wong, DM

Language dc:language

en

Identifier

oai:salford-repository.worktribe.com:1339220

OAI identifier oai:identifier

oai:salford-repository.worktribe.com:1339220