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329
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The origin of the unusual air sensitivity of
OsIIINH2Ph vs. Taube-type coordination complexes is
not the Tp ligand, but rather the involvement of an
aniline ligand. Aniline is much more acidic than am-
monia or alkylamines, so a pathway involving depro-
tonation is much more facile. Deprotonation of the
Os(III) complex lowers the redox potential dramatically,
because the OsIIINHPhꢁ is destabilized by a p conflict
between the anilide pp and Os t2g orbitals while
OsIVNHPh is stabilized by d–p p bonding. With this low
redox potential, ET to dioxygen is roughly thermoneu-
tral and proceeds rapidly.
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J.M. Mayer, in preparation.
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6. Supplementary material
[13] B.K. Bennett, S. Lovell, J.M. Mayer, J. Am. Chem. Soc. 123
(2001) 4336.
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44-1223-
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Acknowledgements
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We are grateful for financial support from the Na-
tional Institutes of Health (R01 GM50422) and from the
National Science Foundation (under Grant Nos.
9816372 and 0204697).
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