The electronic structure of the tris(ethylene) complexes [M(C2H4)3] (M=Ni, Pd, and Pt):: A combined experimental and theoretical study
The electronic structure of the tris(ethylene) complexes [M(C2H4)3] (M=Ni, Pd, and Pt):: A combined experimental and theoretical study
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DOI：
10.1002/chem.200700885
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Scherer, Wolfgang
中科院分区：
文献类型：
--
作者：
Hebben, Nicole;Himmel, Hans-Jorg;Scherer, Wolfgang
本文详细分析了d -3h对称镍、钯、铂三（乙烯）配合物([M（C2H4)(3)] M=Ni, Pd, Pt）的电子性质。在[Pd(C2H4)(3)]的情况下，分析是基于新的实验红外和拉曼光谱的基质分离分子，并在所有情况下基于量子化学（DFT）计算的结果。[Pd(C2H4)(3)]收集的实验光谱为几种以前未观察到的振动模式提供了证据，包括相内和相外nu（C-C）和delta（CH2）模式，以及相内nu（M-C）模式。特别考虑到可能的配体间相互作用。两种C2H4配体之间的相互作用力常数f（CC，CC）可以从光谱中直接估计出来，其很小的值（0.002 Nm(-1)）表明配体之间没有明显的相互作用。对[Pd(C2H4)(3)]及其较轻和较重的同质物[Ni(C2H4)(3)]和[Pt(C2H4)(3)]的理论电子密度分布拓扑rho(r)和相应的拉普拉斯算子del(2)rho(r)的分析，与实验结果的结论完全一致。实验和量子化学结合的结果提供了这些原型乙烯配合物的电子特性的详细见解。
In this article we analyze in detail the electronic properties of the D-3h-Symmetric tris(ethylene) complexes of nickel, palladium, and platinum ([M(C2H4)(3)] M=Ni, Pd, Pt). In the case of [Pd(C2H4)(3)] the analysis is based on new experimental IR and Raman spectra for the matrix-isolated molecules and in all cases on the results of quantum-chemical (DFT) calculations. The experimental spectra collected for [Pd(C2H4)(3)] provide evidence for several previously unobserved vibrational modes, including the in-phase and out-of-phase nu(C-C) and delta(CH2) modes, and the in-phase nu(M-C) mode. Special consideration is given to possible inter-ligand interactions. The interaction force constant f(CC,CC) between two C2H4 ligands can be directly estimated from the spectra, and its very small value (0.002 Nm(-1)) indicates the absence of any significant inter-ligand interaction. An analysis of the topology of the theoretical electron density distribution, rho(r), and the corresponding Laplacian, del(2)rho(r), for [Pd(C2H4)(3)] and its lighter and heavier homologues [Ni(C2H4)(3)] and [Pt(C2H4)(3)], respectively, is in full agreement with the conclusions drawn from the experimental results. The combined experimental and quantum-chemical results provide detailed insights in the electronic properties of these prototypical ethylene complexes.