TY - JOUR
T1 - A Highly Reactive Seven-Coordinate Osmium(V) Oxo Complex
T2 - [OsV(O)(qpy)(pic)Cl]2+
AU - Liu, Yingying
AU - Ng, Siu Mui
AU - Lam, William W.Y.
AU - Yiu, Shek Man
AU - Lau, Tai Chu
N1 - Publisher Copyright:
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/1/4
Y1 - 2016/1/4
N2 - Seven-coordinate ruthenium oxo species have been proposed as active intermediates in catalytic water oxidation by a number of highly active ruthenium catalysts, however such species have yet to be isolated. Reported herein is the first example of a seven-coordinate group 8 metal-oxo species, [OsV(O)(qpy)(pic)Cl]2+ (qpy=2,2′:6′,2″:6″,2⌄-quaterpyridine, pic=4-picoline). The X-ray crystal structure of this complex shows that it has a distorted pentagonal bipyramidal geometry with an Os=O distance of 1.7375 Å. This oxo species undergoes facile O-atom and H-atom-transfer reactions with various organic substrates. Notably it can abstract H atoms from alkylaromatics with C-H bond dissociation energy as high as 90 kcal mol-1. This work suggests that highly active oxidants may be designed based on group 8 seven-coordinate metal oxo species.
AB - Seven-coordinate ruthenium oxo species have been proposed as active intermediates in catalytic water oxidation by a number of highly active ruthenium catalysts, however such species have yet to be isolated. Reported herein is the first example of a seven-coordinate group 8 metal-oxo species, [OsV(O)(qpy)(pic)Cl]2+ (qpy=2,2′:6′,2″:6″,2⌄-quaterpyridine, pic=4-picoline). The X-ray crystal structure of this complex shows that it has a distorted pentagonal bipyramidal geometry with an Os=O distance of 1.7375 Å. This oxo species undergoes facile O-atom and H-atom-transfer reactions with various organic substrates. Notably it can abstract H atoms from alkylaromatics with C-H bond dissociation energy as high as 90 kcal mol-1. This work suggests that highly active oxidants may be designed based on group 8 seven-coordinate metal oxo species.
KW - C-H activation
KW - X-ray diffraction
KW - osmium
KW - oxidation
KW - structure elucidation
UR - http://www.scopus.com/inward/record.url?scp=84955174878&partnerID=8YFLogxK
U2 - 10.1002/anie.201507933
DO - 10.1002/anie.201507933
M3 - Article
AN - SCOPUS:84955174878
SN - 1433-7851
VL - 55
SP - 288
EP - 291
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 1
ER -