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Activation of E–H and E–E (E = S, O) Bonds by Heterobimetallic Zr/Co Complexes: Evidence for Both One‐ and Two‐Electron Processes
Author(s) -
Napoline J. Wesley,
Krogman Jeremy P.,
Shi Rena,
Kuppuswamy Subramaniam,
Bezpalko Mark W.,
Foxman Bruce M.,
Thomas Christine M.
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300122
Subject(s) - chemistry , peroxide , reactivity (psychology) , steric effects , chalcogen , electron transfer , medicinal chemistry , stereochemistry , photochemistry , polymer chemistry , crystallography , organic chemistry , medicine , alternative medicine , pathology
The reactivity of the reduced Zr III Co 0 heterobimetallic complex [(thf)Zr(MesNP i Pr 2 ) 3 CoN 2 ] ( 1a ) towards O–H, S–H, S–S, and O–O bonds has been investigated. Complex 1a reacts readily with PhOH, EtOH, and H 2 O to generate the one‐electron‐oxidized complexes [(RO)Zr(MesNP i Pr 2 ) 3 CoN 2 ] [R = Et ( 2 ), Ph ( 3 ), H ( 4 )]. In contrast, PhSH and PhS–SPh react by means of overall two‐electron processes to form [(η 2 ‐MesNP i Pr 2 )Zr(μ‐SPh)(MesNP i Pr 2 ) 2 Co(SPh)] ( 5a ). Addition of stoichiometric diethyl peroxide to 1a generates 2 , but further equivalents lead to the two‐electron oxidized product [(EtO)Zr(MesNP i Pr 2 ) 3 Co(OEt)] ( 6 ). More sterically hindered peroxides such as dicumyl peroxide or di‐ tert ‐butyl peroxide do not react with 1a under ambient conditions, but upon photolysis, di‐ tert ‐butyl peroxide reacts with 1a to form [( t BuO)Zr(MesNP i Pr 2 ) 3 CoN 2 ] ( 7 ). These results imply that an inner‐sphere electron‐transfer process is occurring at the Zr site of 1a upon treatment with these chalcogen‐based substrates, and a dissociative electron‐transfer mechanism is proposed.