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

Wong, DM 1996, Synthesis, structure and reactivity of chiral cyclopentadienylruthenium(II) complexes , PhD thesis, University of Salford.

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This thesis concerns the preparation, structural, and reactivity studies of new chiral monometallic cyclopentadienylruthenium(n) complexes exhibiting a combination of metal-centred and ligand-derived chirality. The introductory chapter provides an overview of the types of chiral organometallic complexes previously reported, general methods of synthesis, separation, and techniques for stereochemical determination. In the second chapter, a range of chiral cyclopentadienylruthenium(n) amine complexes {[(Ti 5 -C 5 H5)Ru(PPh3 )(L)(NHRR')]PF6 (L = CN*Bu, CO)}, prepared from their precursor halides ((±)-[(rj 5 -C 5 H5)Ru(PPh 3 )(L)X], X = Cl or I) via treatment with various 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 and decomplexations are discussed. The third chapter contains the synthesis and reactions of sulphur donor complexes (dimethyl sulphoxide, (±)-2-methyl-l-butanethiol) which are prepared analogously. 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-methylbenzylisonitrile by 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 known procedures, and the X-ray crystal structure determined for the latter complex is also presented. 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 the alkoxylvinyl or metallated carbene derivatives with iodomethane are discussed for the acyclic and cyclic systems respectively. The sixth chapter contains attempted reactions of the halide precursor and of the molecular 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 seventh chapter. Spontaneous resolution by crystallisation are reported as assayed from X-ray crystal 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.

Item Type: Thesis (PhD)
Contributors: Simpson, SJ (Supervisor)
Schools: Schools > School of Computing, Science and Engineering
Funders: Engineering and Physical Sciences Research Council (EPSRC)
Depositing User: Institutional Repository
Date Deposited: 29 Jun 2021 14:46
Last Modified: 29 Jun 2021 14:46

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