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Chiral diphosphine ligands derived from 1, 4:3, 6-dianhydro-d-mannitol: synthesis, co-ordination to transition metals and catalytic applications.

Fernandez, Cristina Carcedo 2005. Chiral diphosphine ligands derived from 1, 4:3, 6-dianhydro-d-mannitol: synthesis, co-ordination to transition metals and catalytic applications. PhD Thesis, Cardiff University.

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Abstract

The synthesis of a new chiral diphosphine, l,4:3,6-dianhydro-2,5-bis(diphenylphosphino)-D-mannitol (ddppm) is reported, ddppm is derived from the commercially available C2-symmetric l,4:3,6-dianhydro-D-mannitol (Isomannide). This new ligand exhibits a bend butterfly-like geometry with the two-phosphine groups on the concave side. PPh, I PPh, H H ddppm The chelating ability of ddppm is demonstrated with the synthesis of several complexes with transition metals such as Cu, Pd, Pt, Rh, Ru and Ir. Some of these complexes have been successfully crystallized and tested in different catalytic reactions. These complexes haven been characterized and their properties are reported. Their ability to catalyse a range of reactions is also discussed in detail. Chapter 2 reports the synthesis of ddppm. This synthesis requires only two steps with the choice of the solvent being crucial for the formation of this ligand. ddppg, an epimer of ddppm, was also isolated as a by-product from the ddppm synthesis. This diphosphine is a non-chelating ligand unlike ddppm. Crystal structures of both isomers are shown in this chapter. PPh, I H H ddppg: 1,4:3,6-dianhydro-2,5-bis(dipheny lphosphino)-D-glucitol.

Item Type: Thesis (PhD)
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
ISBN: 9781303201431
Date of First Compliant Deposit: 30 March 2016
Last Modified: 11 Nov 2014 12:09
URI: http://orca.cardiff.ac.uk/id/eprint/54551

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