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Virginia Tech

Synthetic Routes to 3-Fold Symmetric Tridentate Oxygen Donor Ligands

Abstract

dc:description.abstract

The class of ligands represented by [CpCo(P(O)(OR)2)3]-, L- , were first synthesized by W. Kläui in 1977. These ligands have been found to coordinate to a variety of low and high oxidation state metals through the use of its three P=O oxygen atoms as donors. The ligands act as mono-anionic six electron donors which make them similar to the more widely known cyclopentadienyl ligands, (C5H5-xRx)-, but have electronic properties like those of fluoride or oxide. Also, it has been found that the coordination chemistry of L- resembles the unsubstituted tris(pryrazolyl)hydroborato six electron ligand, (RB(pz)3)-. All three of these ligands can be modified by changing the substituent R. The Kläui ligand offers a good opportunity to synthesize a chiral derivative. In the process to obtain the chiral version, (cyclopentadienyl)tris(biphenyl-phosphito-P)cobaltate(1-), 18, was synthesized from 2,2'-biphenol. This was characterized through NMR, mass spectroscopy, and XPS. Next, a racemic version, (cyclopentadienyl)tris(biphenylphosphito-P)cobaltate(1-), 17, was synthesized from (±)1,1′-bi-2-naphthol. A one-pot synthesis for the rac-binaphthyl phosphite derivative was developed with an increased yield from the previously published synthesis. The racemic version of the ligand was characterized by NMR and mass spectroscopy. The chiral version has not yet been synthesized, however, by following the developed procedure for the non-chiral version, the ligand could be synthesized from optically active 1,1'-bi-2-naphthol.

Degree

thesis:*
Name thesis:degree_name
Master of Science
Level thesis:degree_level
masters
Discipline thesis:degree_discipline
Chemistry
Department dc:contributor.department
Chemistry
Grantor dc:publisher
Virginia Tech
Year dc:date.issued
1997

Author and committee

dc:creator, dc:contributor.*
Author dc:creator
  • Clevenger, Margo
Chair dc:contributor.committeechair
  • Hanson, Brian E.
Committee members dc:contributor.committeemember
  • Merola, Joseph S.
  • Anderson, Mark R.

Subjects

dc:subject × 5

Rights

dc:rights
Statement dc:rights
  • In Copyright
Language dc:language.iso
en

Identifiers

dc:identifier.*
Dc Identifier Other
etd-7897-122632
OAI identifier oai:identifier
oai:vtechworks.lib.vt.edu:10919/36964

Chain of custody

source
Harvested from
Virginia Tech
Base URL
vtechworks.lib.vt.edu/oai/request
Last updated
2026-07-22
Source record
OAI-PMH GetRecord
citation

Clevenger, Margo. Synthetic Routes to 3-Fold Symmetric Tridentate Oxygen Donor Ligands. masters thesis, Virginia Tech, 1997. http://hdl.handle.net/10919/36964