Electrophilic Addition to η2-Aldehyde Complexes of Pentaammineosmium(II):  The Formation of Fischer Carbyne Complexes via η2-Aldehydium Intermediates

A series of η2-aldehyde complexes of pentaammineosmium(II) of the form [Os(NH3)5(L)](OTf)2 (L = formaldehyde (1), acetaldehyde (2), trimethylacetaldehyde (3), benzaldehyde (4), and crotonaldehyde (5), OTf = trifluoromethanesulfonate) are prepared and characterized. Treatment of these η2-bound aldehy...

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Bibliographic Details
Published in:Journal of the American Chemical Society 1997-12, Vol.119 (52), p.12772-12778
Main Authors: Spera, Michael L, Chen, Huiyuan, Moody, Marcus W, Hill, Maria M, Harman, W. Dean
Format: Article
Language:eng ; jpn
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Summary:A series of η2-aldehyde complexes of pentaammineosmium(II) of the form [Os(NH3)5(L)](OTf)2 (L = formaldehyde (1), acetaldehyde (2), trimethylacetaldehyde (3), benzaldehyde (4), and crotonaldehyde (5), OTf = trifluoromethanesulfonate) are prepared and characterized. Treatment of these η2-bound aldehyde complexes with CH3OTf affords Fischer carbyne complexes 14−18 with typical yields ranging from 25−92%. Protonation (HOTf/MeCN) or methylation (MeOTf/DME) of many of these aldehyde complexes afford O-protonated or O-methylated η2-aldehydium intermediates, respectively, which over time convert to the corresponding carbyne complex. The chemistry of olefin-coordinated α,β-unsaturated aldehyde complexes is also explored.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja972766d