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Article
Synthesis, Characterization, and Reactivity of Group 4 Metalloporphyrin Diolate Complexes
Organometallics
  • Guodong Du, Iowa State University
  • L. Keith Woo, Iowa State University
Document Type
Article
Disciplines
Publication Version
Published Version
Publication Date
1-1-2003
DOI
10.1021/om020790g
Abstract
A number of group 4 metalloporphyrin diolate complexes were synthesized via various approaches. For example, treatment of imido complex (TTP)HfNAriPr with diols resulted in formation of the corresponding diolato complexes (TTP)Hf[OCR1R2CR1R2O] (R1 = R2 = Me, 1; R1 = Me, R2 = Ph, 2; R1 = R2 = Ph, 3). Treatment of (TTP)TiNiPr with diols generated (TTP)Ti[OCR1R2CR1R2O] (R1 = R2 = Me, 5; R1 = Me, R2 = Ph, 6; R1 = H, R2 = Ph, 7; R1 = H, R2= p-tolyl, 8). Alternatively hafnium and titanium pinacolates 1 and 5 were prepared through metathetical reactions of (TTP)MCl2 (M = Hf, Ti) with disodium pinacolate. The substitution chemistry of hafnium complexes correlated well with the basicity of the diolato ligands. Complexes 1−6 underwent oxidative cleavage reaction, producing carbonyl compounds and oxometalloporphyrin species. For less substituted diolates 7 and 8, an array of products including the enediolate complexes (TTP)Ti[OC(Ar)C(Ar)O] (Ar = Ph, 9; Ar = p-tolyl, 10) was observed. The possible cleavage reaction pathways are discussed.
Comments

Reprinted (adapted) with permission from Organometallics 22 (2003): 450, doi:10.1021/om020790g. Copyright 2003 American Chemical Society.

Copyright Owner
American Institute of Physics
Language
en
File Format
application/pdf
Citation Information
Guodong Du and L. Keith Woo. "Synthesis, Characterization, and Reactivity of Group 4 Metalloporphyrin Diolate Complexes" Organometallics Vol. 22 Iss. 3 (2003) p. 450 - 455
Available at: http://works.bepress.com/l-woo/61/