Cationic Two-Coordinate Complexes of Pd(I) and Pt(I) Have Longer Metal-Ligand Bonds Than Their Neutral Counterparts

Journal article


Publication Details

Author(s): Macinnis MC, Demott JC, Zolnhofer E, Zhou J, Meyer K, Hughes RP, Ozerov OV
Journal: Chem
Publication year: 2016
Volume: 1
Journal issue: 6
Pages range: 902-920
ISSN: 2451-9308
eISSN: 2451-9294


Abstract

One-electron oxidation of known (tBu3P)2M (1, M = Pd; 2, M = Pt) with [Ph3C][HCB11Cl11] leads to two-coordinate, monovalent cations of the formula [(tBu3P)2M][HCB11Cl11] (3, M = Pd; 4, M = Pt), which also possess linear geometry but with elongated M--P bonds. Spectroscopic and computational studies consistently show that the unpaired electron of the d9 configuration of 3 and 4 belongs to largely non-bonding orbitals: the s/dz2 hybrid for Pd and the degenerate dx2-y2/dxy pair for Pt. We show that molecular-orbital-based arguments alone are incapable of predicting or rationalizing the observed M--P bond lengthening on oxidation; correct prediction and rationalization are achieved only by inclusion of electrostatic and Pauli effects. This emphasizes the dangers of interpreting any perturbative changes in bond metrics solely on the basis of energies and occupancies of molecular orbitals; the inclusion of electrostatic and Pauli components is essential to providing a more complete picture.


FAU Authors / FAU Editors

Meyer, Karsten Prof. Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Zolnhofer, Eva
Lehrstuhl für Anorganische und Allgemeine Chemie


Additional Organisation
Exzellenz-Cluster Engineering of Advanced Materials


External institutions with authors

Dartmouth College
Harbin Institute of Technology (HIT) / 哈工大
Texas A&M University


Research Fields

D Catalytic Materials
Exzellenz-Cluster Engineering of Advanced Materials


How to cite

APA:
Macinnis, M.C., Demott, J.C., Zolnhofer, E., Zhou, J., Meyer, K., Hughes, R.P., & Ozerov, O.V. (2016). Cationic Two-Coordinate Complexes of Pd(I) and Pt(I) Have Longer Metal-Ligand Bonds Than Their Neutral Counterparts. Chem, 1(6), 902-920. https://dx.doi.org/10.1016/j.chempr.2016.11.007

MLA:
Macinnis, Morgan C., et al. "Cationic Two-Coordinate Complexes of Pd(I) and Pt(I) Have Longer Metal-Ligand Bonds Than Their Neutral Counterparts." Chem 1.6 (2016): 902-920.

BibTeX: 

Last updated on 2019-20-03 at 23:08