Analysis of C-13 and O-17 chemical shift tensors and an ELF view of bonding in Fe-2(CO)(9) and Rh-6(CO)(16)

被引：27

作者：

Kaupp, M ^{[1
]}

机构：

[1] MAX PLANCK INST FESTKORPERFORSCH,D-70569 STUTTGART,GERMANY

来源：

CHEMISCHE BERICHTE | 1996年 / 129卷 / 05期

关键词：

density functional theory; electron localization function; NMR chemical shift tensor; transition-metal carbonyl clusters;

D O I：

10.1002/cber.19961290509

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Carbon and oxygen chemical shift tensors for bridging and terminal carbonyl ligands in Fe-2(CO)(9) and Rh-6(CO)(16) were calculated by sum-over-states density-functional perturbation theory (SOS-DFPT). Agreement with experimental C-13 shift tensors is excellent, and O-17 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 delta(33) 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 Rh-6 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-.

引用

页码：527 / 533

页数：7

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