Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

10-2001

Journal or Book Title

Organometallics

Volume

20

Issue

24

First Page

5189

Last Page

5199

DOI

10.1021/om010787h

Abstract

Catalytic systems derived from [Os(TTP)]2 or Fe(TTP) (TTP = 5,10,15,20-tetra-p-tolylporphyrinato) are extremely efficient at converting styrenes and diazo reagents to cyclopropanes in high yields and high stereoselectivity. A number of mechanistic studies have been undertaken to elucidate the catalytic pathway. A mono(carbene) complex, (TTP)OsCHCO2Et, has been isolated but is not the catalytically active species. An electron-withdrawing ligand trans to the carbene in (TTP)OsCHCO2Et activates the carbon fragment toward transfer to an olefin. Labeling studies with (TTP)OsCHX and N2CHY and substrate reactivity profiles are consistent with a trans-osmium(II) bis(carbene) species as the active catalyst.

Comments

Reprinted (adapted) with permission from Organometallics 20 (2001): 5189, doi:10.1021/om010787h. Copyright 2001 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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