Analysis of 13C and 17O Chemical Shift Tensors and an ELF View of Bonding in Fe2(CO)9 and Rh6(CO)16
- 1 May 1996
- journal article
- research article
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 129 (5) , 527-533
- https://doi.org/10.1002/cber.19961290509
Abstract
Carbon and oxygen chemical shift tensors for bridging and terminal carbonyl ligands in Fe2(CO)9 and Rh6(CO)16 were calculated by sum‐over‐states density‐functional perturbation theory (SOS‐DFPT). Agreement with experimental 13C shift tensors is excellent, and 17O shift tensors are predicted. The reduced anisotropy values of the shift tensors for the bridging compared to terminal carbonyl ligands are due to large deshielding contributions to δ33 from non‐bonding or bridge‐bonding orbitals. Comparison to recent computational results for a series of unusual piano‐stool and bent‐sandwich group‐4 complexes is made. The electronic structures of the clusters are discussed by using plots of electron localization functions (ELF). Bonding electrons within the Rh6 cluster are mainly localized on the unbridged octahedral faces. This leads to a heterocubane‐like arrangement of ELF maxima above all octahedral faces (four bridging CO ligands, four M‐M 3‐center‐bonding maxima), in analogy to previous results for B6H62‐.Keywords
This publication has 48 references indexed in Scilit:
- Ab Initio ECP/DFT Calculation and Interpretation of Carbon and Oxygen NMR Chemical Shift Tensors in Transition‐Metal Carbonyl ComplexesChemistry – A European Journal, 1996
- Scalar Relativistic Effects on 17O NMR Chemical Shifts in Transition-Metal Oxo Complexes. An ab Initio ECP/DFT StudyJournal of the American Chemical Society, 1995
- Unequivocal Partitioning of Crystal Structures, Exemplified by Intermetallic Phases Containing AluminumAngewandte Chemie International Edition in English, 1994
- Die Elektronenlokalisierung in aluminiumhaltigen intermetallischen PhasenAngewandte Chemie, 1994
- Ab initio energy-adjusted pseudopotentials for elements of groups 13–17Molecular Physics, 1993
- Laplacian of charge density for binuclear complexes: terminal vs bridging carbonylsThe Journal of Physical Chemistry, 1993
- Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validationCanadian Journal of Chemistry, 1992
- Energy-adjustedab initio pseudopotentials for the second and third row transition elementsTheoretical Chemistry Accounts, 1990
- High-resolution solid-state oxygen-17 nuclear magnetic resonance spectroscopy of transition metal carbonylsJournal of the Chemical Society, Chemical Communications, 1985
- 13C NMR chemical shift tensors of metal carbonylsThe Journal of Chemical Physics, 1983