Transition Metal Complexes of PNP and PNN Ligands: Synthesis and Catalytic Applications in Hydrophosphination of Terminal Alkynes

IF 3.7 2区 化学 Q2 CHEMISTRY, APPLIED
Khilesh C. Dwivedi, Gazal Sabharwal, Maravanji S. Balakrishna
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引用次数: 0

Abstract

In this study, we report the synthesis and structural characterization of a series of transition metal complexes derived from two pincer-type ligands: {(o-PPh2)C6H4C(O)NH(C9H6N)} (1) and {(o-Ph2PC6H4C(O)N(H)C6H4PPh2-o)} (2). Treatment of Ligand 1 with [Rh (acac)(CO)2] afforded rhodium pincer complex [Rh (CO){(o-PPh2)C6H4C(O)N(C9H6N)}κ3-P,N,N] (3). Ligand 1, upon reaction with [Ru(H)(CO)(Cl)(PPh3)3] in THF, yielded the ruthenium complex [Ru (PPh3)(CO)(Cl){(o-PPh2)C6H4C(O)N(C9H6N)}κ3-P,N,N] (4), while its reaction with [Ru (Cl)2(PPh3)3] in methanol afforded a RuIII complex, [Ru (CH3OH)(Cl)2{(o-PPh2)C6H4C(O) N(C9H6N)}κ3-P,N,N] (5). Ligand 2, when reacted with CuI in a 1:1 M ratio in a CH2Cl2/CH3CN (1:1 v/v) mixture, yielded the dimeric complex [CuI(o-PPh2)C6H4C(O) N(H)CH2C6H4(o-PPh2)]2 (6). Increasing the CuI to ligand ratio to 2:1 yielded the tetrameric complex [Cu4(μ2-I)2(μ3-I)2{(o-PPh2)C6H4C(O)NCH2C6H4 (o-PPh2)}2-P,P] (7). The reaction of Ligand 2 with two equivalents of [AuCl (SMe2)] produced a binuclear gold complex, [AuCl{(o-PPh2)C6H4C(O)N(H)CH2C6H4{(o-PPh2)}AuCl] (8). Furthermore, Ligand 2 underwent complexation with [Rh (acac)(CO)2] and [Mn2(CO)10] to afford PNP-type pincer complexes [RhCO{(o-PPh2)C6H4C(O)NCH2C6H4(o-PPh2)}κ3-P,N,P] (9) and [Mn (CO)3{(o-PPh2)C6H4 C(O)NCH2C6H4(o-PPh2)}κ3-P,N,P] (10) respectively. Notably, the rhodium PNN pincer Complex 3 was successfully employed as a catalyst in the additive-free hydrophosphination of phenylacetylenes, providing a more straightforward and operationally simple methodology for this transformation.

Abstract Image

PNP和PNN配体的过渡金属配合物:合成及其在末端炔烃加氢磷酸化中的催化应用
在本研究中,我们报道了由两个螯合型配体{(O - pph2)C6H4C(O) nhh (C9H6N)}(1)和{(O - ph2pc6h4c (O)N(H)C6H4PPh2-o)}(2)衍生的一系列过渡金属配合物的合成和结构表征。配体1用[Rh (acac)(CO)2]处理得到铑螯合物[Rh (CO){(O - pph2)C6H4C(O)N(C9H6N)}κ3-P,N,N](3)。配体1在THF中与[Ru(H)(CO)(Cl)(PPh3)3]反应生成钌配合物[Ru(PPh3)(CO)(Cl){(O - pph2)C6H4C(O)N(C9H6N))}κ3-P,N,N](4),与[Ru(Cl)2(PPh3)3]在甲醇中反应生成RuIII配合物[Ru(CH3OH)(Cl)2{(O - pph2)C6H4C(O)N(C9H6N)}κ3-P,N,N](5)。配体2与CuI在CH2Cl2/CH3CN (1:1 v/v)混合物中以1:1 M比反应,生成二聚体配合物[CuI(O - pph2)C6H4C(O) N(H)CH2C6H4(O - pph2)]2(6)。将CuI与配体的比例增加到2:1,得到四聚体配合物[Cu4(μ2-I)2(μ3-I)2{(O - pph2)C6H4C(O)NCH2C6H4 (O - pph2)}2-P,P](7)。配体2与[AuCl (SMe2)]的两个等价物反应生成双核金配合物[AuCl{(O - pph2)C6H4C(O)N(H)CH2C6H4{(O - pph2)}AuCl](8)。配体2与[Rh (acac)(CO)2]和[Mn2(CO)10]络合得到pnp型钳形配合物[RhCO{(O - pph2)C6H4C(O)NCH2C6H4(O - pph2)}κ3-P,N,P](9)和[Mn (CO)3{(O - pph2)C6H4C(O)NCH2C6H4(O - pph2)}κ3-P,N,P](10)。值得注意的是,铑PNN钳形配合物3被成功地用作苯乙炔无添加剂加氢磷化的催化剂,为这种转化提供了更直接和操作简单的方法。
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来源期刊
Applied Organometallic Chemistry
Applied Organometallic Chemistry 化学-无机化学与核化学
CiteScore
7.80
自引率
10.30%
发文量
408
审稿时长
2.2 months
期刊介绍: All new compounds should be satisfactorily identified and proof of their structure given according to generally accepted standards. Structural reports, such as papers exclusively dealing with synthesis and characterization, analytical techniques, or X-ray diffraction studies of metal-organic or organometallic compounds will not be considered. The editors reserve the right to refuse without peer review any manuscript that does not comply with the aims and scope of the journal. Applied Organometallic Chemistry publishes Full Papers, Reviews, Mini Reviews and Communications of scientific research in all areas of organometallic and metal-organic chemistry involving main group metals, transition metals, lanthanides and actinides. All contributions should contain an explicit application of novel compounds, for instance in materials science, nano science, catalysis, chemical vapour deposition, metal-mediated organic synthesis, polymers, bio-organometallics, metallo-therapy, metallo-diagnostics and medicine. Reviews of books covering aspects of the fields of focus are also published.
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