Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India.
Univ Rennes, CNRS, Institut des Sciences Chimiques de Rennes, UMR 6226, 35042, Rennes, France.
Chemistry. 2019 Oct 22;25(59):13537-13546. doi: 10.1002/chem.201902663. Epub 2019 Sep 17.
Building upon previous work, the chemistry of [(η -p-cymene)Ru{P(OMe) OR}Cl ], (R=H or Me) has been extended with [H B(mbz) ] (mbz=2-mercaptobenzothiazolyl) using different Ru precursors and borate ligands. As a result, a series of 1,3-N,S-chelated ruthenium borate complexes, for example, [(κ -N,S-L)PR Ru{κ -H,S,S'-H B(L) }], (2 a-d and 2 a'-d'; R=Ph, Cy, OMe or OPh and L=C H NS or C H NS ) and [Ru{κ -H,S,S'-H B(L) } ], (3: L=C H NS, 3': L=C H NS ) were isolated upon treatment of [(η -p-cymene)RuCl PR ], 1 a-d (R=Ph, Cy, OMe or OPh) with [H B(mp) ] or [H B(mbz) ] ligands (mp=2-mercaptopyridyl). All the Ru borate complexes, 2 a-d and 2 a'-d' are stabilized by phosphine/phosphite and hemilabile N,S-chelating ligands. Treatment of these Ru borate species, 2 a'-c' with various terminal alkynes yielded two different types of five-membered ruthenacycle species, namely [PR {C H S -(E)-N-C=CH(R')}Ru{κ -H,S,S'-H B(L) }], (4-4'; R=Ph and R'=CO Me or C H NO ; L=C H NS ) and [PR {C H NS-(E)-S-C=CH(R')}Ru{κ -H,S,S'-H B(L) }], (5-5', 6 and 7; R=Ph, Cy or OMe and R'=CO Me or C H NO ; L=C H NS ). All these five-membered ruthenacycle species contain an exocyclic C=C moiety, presumably formed by the insertion of a terminal alkyne into the Ru-N and Ru-S bonds. The new species have been characterized spectroscopically and the structures were further confirmed by single-crystal X-ray diffraction analysis. Theoretical studies and chemical-bonding analyses established that charge transfer occurs from phosphorus to ruthenium center following the trend PCy <PPh <P(OPh) <P(OMe) .
在之前工作的基础上，通过使用不同的钌前体和硼酸盐配体，扩展了[(η-p-cymene)Ru{P(OMe) OR}Cl ]（R=H 或 Me）的化学性质，得到了一系列 1,3-N,S-螯合的钌硼酸盐配合物，例如[(κ-N,S-L)PR Ru{κ-H,S,S'-H B(L) }]（2a-d 和 2a'-d'；R=Ph、Cy、OMe 或 OPh 和 L=CH NS 或 CH NS ）和[Ru{κ-H,S,S'-H B(L) }]（3：L=CH NS，3'：L=CH NS ）。当用[H B(mp) ]或[H B(mbz) ]配体（mp=2-巯基吡啶基）处理[(η-p-cymene)RuCl PR ]1a-d（R=Ph、Cy、OMe 或 OPh）时，这些[Ru{κ-H,S,S'-H B(L) }]配合物（2a-d 和 2a'-d'）被膦/亚磷酸酯和半配位 N,S-螯合配体稳定。用各种末端炔烃处理这些 Ru 硼酸盐物种 2a'-c'，得到了两种不同类型的五元钌杂环物种，即[PR{C H S -(E)-N-C=CH(R')}Ru{κ-H,S,S'-H B(L) }]（4-4'；R=Ph 和 R'=CO Me 或 C H NO ；L=CH NS ）和[PR{C H NS-(E)-S-C=CH(R')}Ru{κ-H,S,S'-H B(L) }]（5-5'、6 和 7；R=Ph、Cy 或 OMe 和 R'=CO Me 或 C H NO ；L=CH NS ）。所有这些五元钌杂环物种都含有一个外环的 C=C 部分，可能是由末端炔烃插入 Ru-N 和 Ru-S 键形成的。新的物种已经通过光谱学进行了表征，并通过单晶 X 射线衍射分析进一步证实了它们的结构。理论研究和化学键分析表明，电荷从磷向钌中心转移，遵循 PCy<PPh<P(OPh)<P(OMe)的趋势。
