Organoplatinum Chemistry Related to Alkane Oxidation: The Effect of a Nitro Substituent in Ligands Having an Appended Phenol Group

IF 3.1 4区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganics Pub Date : 2024-01-16 DOI:10.3390/inorganics12010032

Anwar Abo-Amer, M. E. Moustafa, Paul D. Boyle, R. Puddephatt

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Abstract

The organoplatinum chemistry of the ligands 2-C5H4N-CH2-NH-C6H3-2-OH-5-X (L1, X = H; L3, X = NO2) and 2-C5H4N-CH=N-C6H3-2-OH-5-X (L2, X = H; L4, X = NO2), which contain an appended phenol substituent, is described. Comparisons are made between the ligands with amine or imine groups (L1, L3 vs. L2, L4) and ligands with X = H or NO2 (L1, L2 vs. L3, L4), and major differences are observed. Thus, on reaction with the cycloneophylplatinum(II) complex [{Pt(CH2CMe2C6H4)(μ-SMe2)}2], ligands L1, L2 and L4 give the corresponding platinum(II) complexes [Pt(CH2CMe2C6H4)(κ2-N,N′-L)], containing a Pt··HO hydrogen bond, whereas L3 gives a mixture of isomeric platinum(IV) hydride complexes [PtH(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)], which are formed by oxidative addition of the phenol O-H bond and which react further with oxygen to give [Pt(OH)(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)]. The differences in reactivity are proposed to be due to the greater acidity of the nitro-substituted phenol groups in L3 and L4 and to the greater ability of the deprotonated amine ligand L3 over L4 to stabilize platinum(IV) by adopting the fac-κ3-N,N′,O-L3-H coordination mode.

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与烷氧化有关的有机铂化学：具有附加苯酚基团的配体中硝基取代基的影响

本文介绍了配体 2-C5H4N-CH2-NH-C6H3-2-OH-5-X（L1，X = H；L3，X = NO2）和 2-C5H4N-CH=N-C6H3-2-OH-5-X（L2，X = H；L4，X = NO2）的有机铂化学性质，其中 2-C5H4N-CH=N-C6H3-2-OH-5-X（L2，X = H；L4，X = NO2）含有一个附加的苯酚取代基。对带有胺或亚胺基团的配体（L1、L3 与 L2、L4）和带有 X = H 或 NO2 的配体（L1、L2 与 L3、L4）进行了比较，发现两者之间存在很大差异。因此，配体 L1、L2 和 L4 与环氧乙基铂（II）络合物 [{Pt(CH2CMe2C6H4)(μ-SMe2)}2] 反应时，会生成相应的铂(II)络合物 [Pt(CH2CMe2C6H4)(κ2-N,N′-L)]，其中含有一个 Pt--HO 氢键、而 L3 则生成一种异构的铂(IV)氢化物络合物[PtH(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)]混合物，这种络合物是由苯酚 O-H 键氧化加成形成的，并与氧气进一步反应生成[Pt(OH)(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)]。据推测，反应活性的差异是由于 L3 和 L4 中硝基取代的苯酚基团具有更强的酸性，以及去质子化的胺配体 L3 比 L4 更能通过采用面-κ3-N,N′,O-L3-H 配位模式来稳定铂(IV)。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganics Chemistry-Inorganic Chemistry

CiteScore

2.80

自引率

10.30%

发文量

193

审稿时长

6 weeks

期刊介绍： Inorganics is an open access journal that covers all aspects of inorganic chemistry research. Topics include but are not limited to: synthesis and characterization of inorganic compounds, complexes and materials structure and bonding in inorganic molecular and solid state compounds spectroscopic, magnetic, physical and chemical properties of inorganic compounds chemical reactivity, physical properties and applications of inorganic compounds and materials mechanisms of inorganic reactions organometallic compounds inorganic cluster chemistry heterogenous and homogeneous catalytic reactions promoted by inorganic compounds thermodynamics and kinetics of significant new and known inorganic compounds supramolecular systems and coordination polymers bio-inorganic chemistry and applications of inorganic compounds in biological systems and medicine environmental and sustainable energy applications of inorganic compounds and materials MD