Oxidation of Methylplatinum(II) Complexes K[(L)Pt II Me] with O 2 and C(sp 3 )-X (X = O and C) Reductive Elimination Reactivity of Methylplatinum(IV) Products ( L )Pt IV Me(OH): The Effect of Structure of Sulfonated CNN-Pincer Ligands L
Oxidation of Methylplatinum(II) Complexes K[(L)Pt II Me] with O 2 and C(sp 3 )-X (X = O and C) Reductive Elimination Reactivity of Methylplatinum(IV) Products ( L )Pt IV Me(OH): The Effect of Structure of Sulfonated CNN-Pincer Ligands L
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甲基铂(II) 络合物 K[(L)Pt II Me] 与 O 2 和 C(sp 3 )-X (X = O 和 C) 的氧化 甲基铂(IV) 产物的还原消除反应性 ( L )Pt IV Me(
DOI：
10.1021/acs.organomet.2c00371
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发表时间：
2022
期刊：
影响因子：
2.8
通讯作者：
Vedernikov, Andrei N.
中科院分区：
文献类型：
--
作者：
Ruan, Jiaheng;Wang, Daoyong;Kramer, Morgan J.;Zavalij, Peter Y.;Vedernikov, Andrei N.
用两个磺化的CNN钳形配体L1和L2研究了以O2和H2O2为氧化剂(HL1-=(6-phenylpyrid-2-yl)(pyrid-2-yl)methanesulfonate；HL2-=(6-phenylpyrid-2-yl)-6，7-dihydro-5H-cyclopenta[b]吡啶-7-磺酸盐)衍生的K[(L)PtIIMe]配合物(L=L1和L2)中PtII-Me键的氧化官能化.K[(L1)PtIIMe]在甲醇中用O2氧化生成单一的高价铂配合物，(L1)PtIVMe2，而使用过氧化氢得到(L1)PtIVMe(OH)，10c和(L1)2PtIV2Me2(μ-OH)2，14，具有不同构型的PtIV中心。更刚性的类似物K[(L2)PtIIMe]与O2氧化生成非对映异构体(L2)PtIVMe(OH)，11d在甲醇中，11a(作为CF3CH2O-阴离子的加合物)在丙酮/2，2，2-三氟乙醇的混合物中被检测到。在H_2O_2的作用下，得到了(L2)PtIVMe(OH)，11c和(L2)2PtIV2Me2(μ-OH)2，15，类似物10和14。当与CF3CO2H在DMSO、MeOH或丙酮的水溶液中于80°C加热时，(L)PtIVMe(OH)络合物高产率地生成MeOH和MeO_2CCF_3或C(Sp2)-C(Sp3)偶联产物，涉及钳形配体的碳原子。用密度泛函理论计算分析了观察到的反应性。结果表明，有利于C(SP3)-O偶联的关键因素是甲基配体和磺酸基的反式排列，使用CF3CO2-作为O-亲核剂，使用DMSO作为溶剂有利于生成高度亲电的PtIVMe中间体。
Two sulfonated CNN-pincer ligands L1 and L2 were used to explore the oxidative functionalization of the PtII-Me bond in derived K[(L)PtIIMe] complexes (L = L1 and L2) using O2and H2O2as oxidants (HL1–= (6-phenylpyrid-2-yl)(pyrid-2-yl)methanesulfonate; HL2–= (6-phenylpyrid-2-yl)-6,7-dihydro-5H-cyclopenta [b]pyridine-7-sulfonate). Oxidation with O2of K[(L1)PtIIMe] in MeOH produced a single high-valent platinum complex, (L1)PtIVMe2, whereas the use of H2O2led to (L1)PtIVMe(OH),10c, and (L1)2PtIV2Me2(μ-OH)2,14, having different configurations of a PtIVcenter. Oxidation of a more rigid analog, K[(L2)PtIIMe], with O2led to diastereomeric complexes (L2)PtIVMe(OH),11d, in MeOH and11a(detected as an adduct with the CF3CH2O–anion) in acetone/2,2,2-trifluoroethanol mixtures. The use of H2O2led to (L2)PtIVMe(OH),11c, and (L2)2PtIV2Me2(μ-OH)2,15, the analogs of10cand14, respectively. When heated with CF3CO2H in aqueous DMSO, MeOH, or acetone at 80 °C, (L)PtIVMe(OH) complexes produced in high yield either MeOH and MeO2CCF3or C(sp2)-C(sp3) coupled products involving a carbon atom of pincer ligands. DFT calculations were used to analyze the observed reactivity. It was concluded that the key factors favoring the C(sp3)-O coupling are thetrans-arrangement of the methyl ligand and the sulfonate group, the use of CF3CO2–as an O-nucleophile and DMSO as a solvent favoring the generation of highly electrophilic PtIVMe intermediates.