TY - JOUR
T1 - Electronic and Geometric Structures of Pt(NH3)22+, Pt(NH3)2Cl2, Pt(NH3)3X, and Pt(NH3)2XY (X, Y = H2O, OH)
AU - Basch, Harold
AU - Krauss, M.
AU - Stevens, W. J.
AU - Cohen, Drora
PY - 1985/10/1
Y1 - 1985/10/1
N2 - Isomeric energies and conformations for Pt(NH3)22+ (DP), Pt(NH3)2Cl2 (DDP), Pt(NH3)3X, and Pt(NH3)2XY (X = NH3, H2O, OH-; Y = H2O, OH-) have been calculated by ab initio molecular orbital theory using energy gradient methods. The trends in metal-ligand bond lengths follow a consistent pattern that permits the development of a trans-influence ordering of ligands. The OH- ligand is predicted to be in an unusual position in this ordering. However, the experimentally derived ordering schemes may not have been examining the bare hydroxy species, which is found to seek out hypervalent hydrogen-bonded attachments. The Pt(NH3)22+ fragment is found to have a locally stable "cis" conformation, but the trans-DP and all the trans-Pt(NH3)2XY complexes with X, Y = H2O, OH- are lower in energy than the cis. However, with the ionic ligands, CI and OH, strong hydrogen bonds are obtained for favorable geometric configurations. When these bonds are formed, little difference is found between the energies of the cis and trans isomers.
AB - Isomeric energies and conformations for Pt(NH3)22+ (DP), Pt(NH3)2Cl2 (DDP), Pt(NH3)3X, and Pt(NH3)2XY (X = NH3, H2O, OH-; Y = H2O, OH-) have been calculated by ab initio molecular orbital theory using energy gradient methods. The trends in metal-ligand bond lengths follow a consistent pattern that permits the development of a trans-influence ordering of ligands. The OH- ligand is predicted to be in an unusual position in this ordering. However, the experimentally derived ordering schemes may not have been examining the bare hydroxy species, which is found to seek out hypervalent hydrogen-bonded attachments. The Pt(NH3)22+ fragment is found to have a locally stable "cis" conformation, but the trans-DP and all the trans-Pt(NH3)2XY complexes with X, Y = H2O, OH- are lower in energy than the cis. However, with the ionic ligands, CI and OH, strong hydrogen bonds are obtained for favorable geometric configurations. When these bonds are formed, little difference is found between the energies of the cis and trans isomers.
UR - http://www.scopus.com/inward/record.url?scp=0022341199&partnerID=8YFLogxK
U2 - 10.1021/ic00215a002
DO - 10.1021/ic00215a002
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AN - SCOPUS:0022341199
SN - 0020-1669
VL - 24
SP - 3313
EP - 3317
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -