Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

3-2004

Journal or Book Title

Inorganic Chemistry

Volume

43

Issue

7

First Page

2379

Last Page

2386

DOI

10.1021/ic035123+

Abstract

Reactions of tin porphyrins with vicinal diols were investigated. Treatment of (TTP)Sn(C⋮CPh)2or (TTP)Sn(NHtolyl)2 with pinacol and 2,3-diphenylbutane-2,3-diol afforded diolato complexes (TTP)Sn[OC(Me)2C(Me)2O] (1) and (TTP)Sn[OC(Ph)(Me)C(Ph)(Me)O] (2), respectively. Both complexes underwent C−C cleavage reactions to give (TTP)SnII and ketones. Reaction of (TTP)Sn(C⋮CPh)2 with 1 equivalent of o-catechol generated (TTP)Sn(C⋮CPh)(OC6H4OH) (3), which subsequently transformed into (TTP)Sn(OC6H4O) (4). With excess catechol, disubstituted (TTP)Sn(OC6H4OH)2 (5) was obtained. (TTP)Sn(C⋮CPh)(OCHRCHROH) (R = H, 6; R = Ph, 8) and (TTP)Sn(OCHRCHROH)2 (R = H, 7; R = Ph, 9) were obtained analogously by treatment of (TTP)Sn(C⋮CPh)2 with appropriate diols. In the presence of dioxygen, tin porphyrin complexes were found to promote the oxidative cleavage of vicinal diols and the oxidation of α-ketols to α-diketones. Possible reaction mechanisms involving diolato or enediolato intermediates are discussed. The molecular structure of (TTP)Sn(C⋮CPh)(OC6H4OH) (3) was determined by X-ray crystallography.

Comments

Reprinted (adapted) with permission from Inorganic Chemistry 43 (2004): 2379, doi:10.1021/ic035123+. Copyright 2004 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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