Chemistry and biology of tricarbonyl complexes of technetium and rhenium

Chapter One: Two of the most famous tripodal ligands, Kliui's cyclopentadienyltris(dialkylphosphito)cobaltate(III) and Trofimenko's hydrotris(1-pyrazolyl)borate, were studied with respect to their reactivity towards Alberto's tris(solvento)tricarbonyltechnetium(I) and tris(solvento)tricarbonylrhenium(I) cations. The reaction of [M(H2O)3(CO)3]+ (M = Tc, Re) with Na[CpCo[PO(OR)2]3] (NaLOR; R = Me, Et) in water produced the compounds M(CO)3(LoR). The two compounds M(CO)3(LoEt) were structurally characterized by single crystal X-ray crystallography. In both cases, the ligand LOEt was bound to the metal center in a tridentate fashion utilizing an 000 donor set. The ligands LOR can be used as models for facially coordinated triaqua groups owing to their position in the spectrochemical series. Therefore, these four compounds, M(CO)3(LoR), can be considered structural models for [M(H2O)3(CO)3]+. The reaction of [Re(CO)3(sol)3]+ (sol = H20, MeOH, MeCN) with K[HB(pz)3] (KTp) has yielded a variety of products depending on the solvent used. For the two protic solvents, mixtures of TpRe(CO)3 and a byproduct (NEt4)[Re2(CO)6(jg-pz)2([t-OR)] (R = H or Me) were obtained. The methoxy-bridged species has been isolated and fully characterized, and the crystal structure has been determined. While a chemical separation of the analogous hydroxy-bridged species from TpRe(CO)3 was not accomplished, a crystal of the compound was selected from the mixture, and a partial crystal structure was solved. When an aprotic solvent such as acetonitrile was used, only TpRe(CO)3 was obtained and was recovered in high yield.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2003

Author dc:creator

• Kramer, Daniel Joshua, 1977-

Advisor dc:contributor.advisor

• Alan Davison.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/29640

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/29640