X-ray crystallography and electrochemistry reveal electronic and steric effects of phosphine and phosphite ligands in complexes RuII(κ4-bda)(PR3)2 and RuII(κ3-bda)(PR3)3 (bda = 2,2′-bipyridine-6,6′-dicarboxylato)
X-ray crystallography and electrochemistry reveal electronic and steric effects of phosphine and phosphite ligands in complexes RuII(κ4-bda)(PR3)2 and RuII(κ3-bda)(PR3)3 (bda = 2,2′-bipyridine-6,6′-dicarboxylato)
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X 射线晶体学和电化学揭示了配合物 RuII(γ4-bda)(PR3)2 和 RuII(γ3-bda)(PR3)3 (bdaầ=ầ2,2â) 中膦和亚磷酸酯配体的电子和空间效应
DOI：
10.1016/j.poly.2018.12.033
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发表时间：
2019
期刊：
影响因子：
2.6
通讯作者：
Grotjahn, Douglas B.
中科院分区：
文献类型：
--
作者：
Yazdani, Sima;Silva, Braden E.;Cao, Thomas C.;Rheingold, Arnold L.;Grotjahn, Douglas B.
我们已经研究了协调PR 3 =三苯基膦，三乙基膦，三异丙基亚磷酸酯，亚磷酸三甲酯，和1，3，5-三氮杂-7-磷杂金刚烷（PTA）的片段钌II（bda），以更好地了解如何不同的膦和亚磷酸酯配体的影响的电子和结构性质的钌II配合物。PTA和P（OMe）3得到了三个磷配体与Ru结合的配合物，其中bda在配合物4和5中是三齿的（κ3-N，N，O）;对于其他三个磷配体，即使在大于2当量的存在下，也只观察到RuII（κ4-bda）（PR 3）2物种1 - 3。实验和计算的方法被用来研究的配合物。空间效应是决定是否形成二或三（PR 3）络合物的主要因素。循环伏安法研究的配合物显示，在RuIII/II电位增加后，有另一个磷配体在赤道位置。计算研究预测，额外的膦配体在赤道平面的4从事显着的轨道混合与钌中心，导致较低的能量结合相比，轴向膦配体。这项工作提供了第一次评估磷配体的空间和电子效应的RuII（BDA）片段。
We have examined coordination of PR3= triphenylphosphine, triethylphosphine, triisopropyl phosphite, trimethyl phosphite, and 1,3,5-triaza-7-phosphaadamantane (PTA) to the fragment RuII(bda) to better understand how different phosphine and phosphite ligands influence the electronic and structural properties of the RuIIcomplexes. PTA and P(OMe)3afforded complexes with three phosphorus ligands bound to Ru, with the bda being tridentate (κ3-N,N,O) in complexes4and5; for the other three phosphorus ligands, even in the presence of >2 equiv, only RuII(κ4-bda)(PR3)2species1–3were seen. Both experimental and computational methods were used to study the complexes. Steric effects are the main factor determining whether bis- or tris(PR3) complexes are formed. Cyclic voltammetry studies of the complexes revealed an increase in RuIII/IIpotential upon having another phosphorus ligand in the equatorial position. Computational studies predict that the additional phosphine ligand in the equatorial plane of4engages in significant orbital mixing with the ruthenium center that results in lower energy bonding as compared to the axial phosphine ligands. This work provides the first evaluation of phosphorus ligand steric and electronic effects on the RuII(bda) fragment.
影响因子：
21.8
作者：
Duan, Lele;Bozoglian, Fernando;Sun, Licheng
通讯作者：
Sun, Licheng
影响因子：
4.6
作者：
Darensbourg, DJ;Robertson, JB;Reibenspies, JH
通讯作者：
Reibenspies, JH