Synthesis and Structural Studies of Cationic Bis- and Tris(pyrazol-1-yl)methane Acyl and Methyl Complexes of Ruthenium(II): Localization of the Counterion in Solution by NOESY NMR Spectroscopy
Synthesis and Structural Studies of Cationic Bis- and Tris(pyrazol-1-yl)methane Acyl and Methyl Complexes of Ruthenium(II): Localization of the Counterion in Solution by NOESY NMR Spectroscopy
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钌(II)阳离子双和三(吡唑-1-基)甲烷酰基和甲基配合物的合成和结构研究：通过 NOESY NMR 光谱定位溶液中的抗衡离子
DOI：
10.1021/om980631q
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发表时间：
1998
期刊：
影响因子：
2.8
通讯作者：
C. Zuccaccia
中科院分区：
文献类型：
--
作者：
A. Macchioni;G. Bellachioma;G. Cardaci;G. Cruciani;E. Foresti;P. Sabatino;C. Zuccaccia
配合物fac-Ru（PMe 3）（CO）3（Me）I（1）在NaBPh 4存在下与三和双（吡唑-1-基）甲烷反应，分别得到顺式-[Ru（PMe 3）（CO）2（COMe）（η2-pz 3-CH）] BPh 4（2）和顺式-[Ru（PMe 3）（CO）2（COMe）（pz 2-CH 2）] BPh 4（4）。配合物2和4脱羰基，分别得到[Ru（PMe 3）（CO）（COMe）（η3-pz 3-CH）] BPh 4（3）和顺式-[Ru（PMe 3）（CO）2（Me）（pz 2-CH 2）] BPh 4（5−7）的三种甲基立体异构体的混合物。合成1的副产物fac，cis-Ru（PMe 3）（CO）3（I）2（8），与双（吡唑-1-基）甲烷反应得到cis-[Ru（PMe 3）（CO）2（I）（pz 2-CH 2）] BPh 4（9）。配合物的立体化学，它们之间存在的动力学过程，和所有的阳离子配合物的电子结构进行了研究，通过相敏的1H NOESY NMR谱在CD 2Cl 2。通过单晶X射线研究获得的4的固态晶体结构，从分子内和电子的角度与溶液中的3- 21 G * ab initio和AMI-SM 2半经验方法进行了比较。
Complex fac-Ru(PMe3)(CO)3(Me)I (1) reacts with tris- and bis(pyrazol-1-yl)methane, in the presence of NaBPh4, affording cis-[Ru(PMe3)(CO)2(COMe)(η2-pz3-CH)]BPh4 (2) and cis-[Ru(PMe3)(CO)2(COMe)(pz2-CH2)]BPh4 (4), respectively. Complexes 2 and 4 decarbonylate leading to [Ru(PMe3)(CO)(COMe)(η3-pz3-CH)]BPh4 (3) and a mixture of three methyl stereoisomers of cis-[Ru(PMe3)(CO)2(Me)(pz2-CH2)]BPh4 (5−7), respectively. The byproduct of the synthesis of 1, fac,cis-Ru(PMe3)(CO)3(I)2 (8), reacts with bis(pyrazol-1-yl)methane affording cis-[Ru(PMe3)(CO)2(I)(pz2-CH2)]BPh4 (9). The stereochemistry of the complexes, the dynamic processes existing between them, and the interionic structures of all of the cationic complexes were investigated by the phase-sensitive 1H NOESY NMR spectra in CD2Cl2. The solid-state crystal structure of 4, obtained by single-crystal X-ray studies, was compared from the intramolecular and interionic point of views with that in solution with the help of 3-21G* ab initio and AMI−SM2 semiempirical...