TY - JOUR
T1 - Revisiting Ir(CO)3Cl
AU - Tsuji, Yuta
AU - Hoffmann, Roald
AU - Miller, Joel S.
N1 - Funding Information:
Y.T. thanks the Japan Society for the Promotion of Science for a JSPS Postdoctoral Fellowship for Research Abroad. Our work at Cornell was supported by the National Science Foundation through Grant CHE-1305872 .
Publisher Copyright:
© 2015 Elsevier Ltd. All rights reserved.
PY - 2016/1/8
Y1 - 2016/1/8
N2 - We return to an old puzzle - the short metal-metal separation and electrical conductivity of the apparently unoxidized one-dimensionally stacked structure of a d8 Ir(I) complex, Ir(CO)3Cl. One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d8 array. We build up dimer, trimer, one-dimensional polymer and model 3-dimensional structures, in both molecular and extended structure plane wave calculations. The short Ir-Ir separation in the polymer, with a substantial contribution of 6pz-5dz2 bonding to it, is obtained without any oxidation. There is computational evidence for an important level crossing in the polymer. The metallicity remains unexplained, but likely arises from partial oxidation. And that remains an outstanding experimental issue.
AB - We return to an old puzzle - the short metal-metal separation and electrical conductivity of the apparently unoxidized one-dimensionally stacked structure of a d8 Ir(I) complex, Ir(CO)3Cl. One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d8 array. We build up dimer, trimer, one-dimensional polymer and model 3-dimensional structures, in both molecular and extended structure plane wave calculations. The short Ir-Ir separation in the polymer, with a substantial contribution of 6pz-5dz2 bonding to it, is obtained without any oxidation. There is computational evidence for an important level crossing in the polymer. The metallicity remains unexplained, but likely arises from partial oxidation. And that remains an outstanding experimental issue.
UR - http://www.scopus.com/inward/record.url?scp=84948775723&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84948775723&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2015.09.050
DO - 10.1016/j.poly.2015.09.050
M3 - Article
AN - SCOPUS:84948775723
VL - 103
SP - 141
EP - 149
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -