Structure and bonding energy analysis of M-Ga bonds in dihalogallyl complexes trans-[X(PMe3)2M(GaX2)] (M = Ni, Pd, Pt; X = Cl, Br, I).
Structure and bonding energy analysis of M-Ga bonds in dihalogallyl complexes trans-[X(PMe3)2M(GaX2)] (M = Ni, Pd, Pt; X = Cl, Br, I).
复制标题
二卤代烯丙基配合物反式-[X(PMe3)2M(GaX2)]（M = Ni、Pd、Pt；X = Cl、Br、I）中 M-Ga 键的结构和键能分析。
DOI：
10.1021/ic1005506
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发表时间：
2010
影响因子：
4.6
通讯作者：
H. Braunschweig
中科院分区：
文献类型：
--
作者：
K. Pandey;Pankaj Patidar;H. Braunschweig
在 BP86 理论水平上研究了镍、钯和铂反式-[X(PMe(3))(2)M(GaX(2))]（M = Ni、Pd、Pt；X = Cl、Br、I）的末端中性二卤代烯丙基配合物的几何结构、电子结构和成键分析。铂没食子配合物反式-[X(PMe(3))(2)Pt(GaX(2))] (X = Br, I)的计算几何形状与结构特征铂配合物反式-[X(PCy(3))(2)M(GaX(2))]非常一致。在镍和钯的没食子配合物中，M-Ga 西格玛键轨道稍微偏向镓原子，而在铂没食子配合物中，M-Ga西格玛键轨道稍微偏向铂原子。值得注意的是，沿着 M-Ga 西格玛键的镓原子具有较大的 p 特征，其总是 > AO 贡献总量的 51%，而沿着 Ga-X 西格玛键，p 特征从 72% 到 73% 变化。尽管 M-Ga pi 键合非常小，但 M-Ga 键距很短，这是由于沿着 M-Ga 键的镓的大 s 特性（大约 45-48%）。计算的 NPA 电荷分布表明金属原子带有负电荷，Ga 原子带有大量正电荷。在所有没食子络合物中，静电相互作用项 DeltaE(elstat) 的贡献明显大于共价键 DeltaE(orb) 项。因此，所研究的 Ni、Pd 和 Pt 没食子络合物中的 [M]-GaX(2) 键具有更大程度的离子特征 (65.7-72.5%)。在所有配合物中，π键的贡献明显小于西格玛键的贡献。在GaX(2)配体中，镓主要充当西格玛供体。所有三组配合物中的相互作用能均按 Ni < Pd < Pt 的顺序增加，并且在所有三组配合物中，DeltaE(Pauli)、DeltaE(int) 和 DeltaE(elstat) 对 M-Ga 键贡献的绝对值均按 X = Cl < Br < I 的顺序减少。
Geometry, electronic structure, and bonding analysis of the terminal neutral dihalogallyl complexes of nickel, palladium, and platinum trans-[X(PMe(3))(2)M(GaX(2))] (M = Ni, Pd, Pt; X = Cl, Br, I) were investigated at the BP86 level of theory. The calculated geometries of platinum gallyl complexes trans-[X(PMe(3))(2)Pt(GaX(2))] (X = Br, I) are in excellent agreement with structurally characterized platinum complexes trans-[X(PCy(3))(2)M(GaX(2))]. In the gallyl complexes of nickel and palladium, the M-Ga sigma bonding orbital is slightly polarized toward the gallium atom, while in the platinum gallyl complexes, the M-Ga sigma bonding orbital is slightly polarized toward the platinum atom. It is significant to note that gallium atoms along the M-Ga sigma bonds have large p character, which is always >51% of the total AO contributions, while along the Ga-X sigma bonds, the p character varies from 72% to 73%. The short M-Ga bond distances, in spite of the significantly small M-Ga pi bonding, are due to the large s character of gallium (approximately 45-48%) along the M-Ga bonds. The calculated NPA charge distributions indicate that the metal atom carries negative charge and the Ga atom carries significantly large positive charge. The contributions of the electrostatic interaction terms, DeltaE(elstat), are significantly larger in all gallyl complexes than the covalent bonding DeltaE(orb) term. Thus, the [M]-GaX(2) bond in the studied gallyl complexes of Ni, Pd, and Pt has a greater degree of ionic character (65.7-72.5%). The pi-bonding contribution is, in all complexes, significantly smaller than the sigma bonding contribution. In the GaX(2) ligands, gallium dominantly behaves as a sigma donor. The interaction energy increases in all three sets of complexes via order of Ni < Pd < Pt, and the absolute value of DeltaE(Pauli), DeltaE(int), and DeltaE(elstat) contributions to the M-Ga bonds decreases via X = Cl < Br < I in all three sets of complexes.