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High Selectivity in Csp2–Csp2 versus Csp3–O Reductive Elimination from Cycloplatinated(IV) Complexes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-06-22 , DOI: 10.1021/acs.inorgchem.4c01096
Marzieh Dadkhah Aseman 1 , Susan Kiyavash 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-06-22 , DOI: 10.1021/acs.inorgchem.4c01096
Marzieh Dadkhah Aseman 1 , Susan Kiyavash 1
Affiliation
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The cycloplatinated(IV) complexes trans-[Pt(p-MeC6H4)(C∧N)(OAc)2(H2O)] (C∧N = benzo[h]quinolate, bhq, 2a, and 2-phenylpyridinate, ppy, 2b) were prepared by reacting the corresponding [Pt(p-MeC6H4)(C∧N)(SMe2)] precursors with PhI(OAc)2 through an oxidative addition (OA) reaction. Thermolysis of 2a at 65 °C generates cis-[Pt(κ1N-10-(p-MeC6H4)-bhq)(OAc)2(H2O)], 3a, which is the product of a Csp2Ar–Csp2bhq reductive elimination (RE). The observed coupling reaction is significantly different from the previously reported analogous thermolysis of trans-[PtMe(C∧N)(OAc)2(H2O)] (C∧N = bhq, 2c, and ppy, 2d) that selectively releases Me–OAc (C–O RE). The density functional theory (DFT) calculations and experimental observations reveal that the Csp2Ar–Csp2bhq coupling reaction occurs through the dissociation of a coordinated water ligand. This in turn is followed by the concomitant bond forming and bond breaking process via a three-center ring transition state, in contrast to the Csp3Me–OAc coupling, which had taken place by an outer sphere SN2 type RE reaction in methyl complexes.
中文翻译：
环铂 (IV) 配合物中 Csp2–Csp2 与 Csp3–O 还原消除的高选择性
环铂(IV)络合物反式-[Pt( p -MeC 6 H 4 )(C ∧ N)(OAc) 2 (H 2 O)] (C ∧ N = 苯并[h]喹啉、bhq、 2a和 2 -苯基吡啶酸酯，ppy， 2b ）是通过相应的[Pt（ p -MeC 6 H 4 ）（C ∧ N）（SMe 2 ）]前体与PhI（OAc） 2通过氧化加成（OA）反应制备的。 2a在 65 °C 下热解生成cis -[Pt(κ 1 N-10-( p -MeC 6 H 4 )-bhq)(OAc) 2 (H 2 O)], 3a ，它是 Csp 的产物2 Ar –Csp 2 bhq还原消除 (RE)。观察到的偶联反应与先前报道的选择性释放反式-[PtMe(C ∧ N)(OAc) 2 (H 2 O)] (C ∧ N = bhq, 2c和 ppy, 2d ) 的类似热解显着不同Me-OAc (C-O RE)。密度泛函理论（DFT）计算和实验观察表明，Csp 2 Ar -Csp 2 bhq偶联反应是通过配位水配体的解离发生的。接下来是通过三中心环过渡态伴随的成键和断键过程，与 Csp 3 Me -OAc 偶联相反，Csp 3 Me -OAc 偶联是通过甲基中的外球 S N 2 型 RE 反应发生的复合物。
更新日期：2024-06-22
中文翻译：
环铂 (IV) 配合物中 Csp2–Csp2 与 Csp3–O 还原消除的高选择性
环铂(IV)络合物反式-[Pt( p -MeC 6 H 4 )(C ∧ N)(OAc) 2 (H 2 O)] (C ∧ N = 苯并[h]喹啉、bhq、 2a和 2 -苯基吡啶酸酯，ppy， 2b ）是通过相应的[Pt（ p -MeC 6 H 4 ）（C ∧ N）（SMe 2 ）]前体与PhI（OAc） 2通过氧化加成（OA）反应制备的。 2a在 65 °C 下热解生成cis -[Pt(κ 1 N-10-( p -MeC 6 H 4 )-bhq)(OAc) 2 (H 2 O)], 3a ，它是 Csp 的产物2 Ar –Csp 2 bhq还原消除 (RE)。观察到的偶联反应与先前报道的选择性释放反式-[PtMe(C ∧ N)(OAc) 2 (H 2 O)] (C ∧ N = bhq, 2c和 ppy, 2d ) 的类似热解显着不同Me-OAc (C-O RE)。密度泛函理论（DFT）计算和实验观察表明，Csp 2 Ar -Csp 2 bhq偶联反应是通过配位水配体的解离发生的。接下来是通过三中心环过渡态伴随的成键和断键过程，与 Csp 3 Me -OAc 偶联相反，Csp 3 Me -OAc 偶联是通过甲基中的外球 S N 2 型 RE 反应发生的复合物。
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