Polyhedral Flexibility in the Sulfido-Capped Cluster H 2 Ru 3 (CO) 9 (μ 3 -S) on Reaction with 2-(Diphenylphosphino)thioanisole (PS) and Reversible Tripodal Rotation of the Chelated PS Ligand in H 2 Ru 3 (CO) 7 (κ 2 -PS)(μ 3 -S)
Polyhedral Flexibility in the Sulfido-Capped Cluster H 2 Ru 3 (CO) 9 (μ 3 -S) on Reaction with 2-(Diphenylphosphino)thioanisole (PS) and Reversible Tripodal Rotation of the Chelated PS Ligand in H 2 Ru 3 (CO) 7 (κ 2 -PS)(μ 3 -S)
复制标题
硫基封端簇 H 2 Ru 3 (CO) 9 (μ 3 -S) 与 2-(二苯基膦)硫代苯甲醚 (PS) 反应的多面体灵活性以及螯合 PS 配体在 H 2 Ru 3 (CO) 中的可逆三足旋转
DOI：
10.1021/acs.organomet.9b00202
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
Richmond, Michael G.
中科院分区：
文献类型：
--
作者：
Mayberry, Darrell D.;Nesterov, Vladimir N.;Richmond, Michael G.
用2-（二苯基膦基）茴香硫醚（PS）处理四面体簇合物H2 Ru 3（CO）9（μ3-S）（1），得到了H2 Ru 3（CO）7（κ2-PS）（μ3-S）（2）。配合物2是一对非对映异构体，在298 K时Keq = 1.55，配体在Ru（CO）（κ2-PS）中心的位置不同。PS配体占据的赤道网站（Peq，Seq）的动力学异构体和轴向和赤道网站（Pax，Seq）中的philically青睐的物种。用X射线衍射分析确定了2的动力学异构体的固态结构，用NMR和HPLC测定了293-323 K温度范围内的可逆一级平衡动力学。用密度泛函理论计算了1的取代反应和2中PS配体的异构化反应。计算结果支持膦诱导的簇多面体的膨胀，这是由PS供体到1的缔合加成引发的。1中的顶点选择性打开，导致一个桥联的Ru-Ru键断裂，生成膦取代的簇合物H2 Ru 3（CO）9（κ1-PS）（μ3-S）作为初始加合物.侧接的MeS部分的螯合伴随CO的损失，得到动力学取代产物H2 Ru 3（CO）7（κ2-Peq，Seq）（μ3-S）（2）。在2中观察到的PS配体的异构化最好解释为在Ru（CO）（κ2-PS）中心的CO和PS基团的三脚架旋转，其之前是2中的一个边缘桥接键向非桥接Ru-Ru键的区域特异性迁移。
Treatment of the tetrahedral cluster H2Ru3(CO)9(μ3-S) (1) with 2-(diphenylphosphino)thioanisole (PS) furnishes the cluster H2Ru3(CO)7(κ2-PS)(μ3-S) (2). Cluster2, which exhibits a chelated thiophosphine ligand (κ2-PS), exists as a pair of diastereomers withKeq= 1.55 at 298 K that differ in their disposition of ligands at the Ru(CO)(κ2-PS) center. The PS ligand occupies the equatorial sites (Peq,Seq) in the kinetic isomer and axial and equatorial sites (Pax,Seq) in the thermodynamically favored species. The solid-state structure of the kinetic isomer of2has been established by X-ray diffraction analysis, and the reversible first-order kinetics to equilibrium have been measured experimentally by NMR spectroscopy and HPLC over the temperature range 293–323 K. The substitution reaction involving1and the isomerization of the PS ligand in2were investigated by DFT calculations. The computational results support a phosphine-induced expansion of the cluster polyhedron that is triggered by the associative addition of the PS donor to1. The vertex opening in1is selective and leads to the cleavage of a hydride-bridged Ru–Ru bond to give the phosphine-substituted cluster H2Ru3(CO)9(κ1-PS)(μ3-S) as the initial adduct. Chelation of the pendant MeS moiety follows with a loss of CO to give the kinetic substitution product H2Ru3(CO)7(κ2-Peq,Seq)(μ3-S) (2). The observed isomerization of the PS ligand in2is best explained by a tripodal rotation of the CO and PS groups at the Ru(CO)(κ2-PS) center that is preceded by a regiospecific migration of one of the edge-bridging hydrides to the nonhydride-bridged Ru–Ru bond in2.