Cross-Coupling versus Homo-Coupling at a Pt(IV) Center: Computational and Experimental Approaches

被引：3

作者：

Bavi, Marzieh ^{[1
]}

Nabavizadeh, S. Masoud ^{[1
]}

Hosseini, Fatemeh Niroomand ^{[3
]}

Hoseini, S. Jafar ^{[1
]}

Friedel, Joshua Nicolas ^{[1
,2
]}

Klein, Axel ^{[2
]}

机构：

[1] Shiraz Univ, Coll Sci, Dept Chem, Prof Rashidi Lab Organometall Chem, Shiraz 7146713565, Iran

[2] Univ Cologne, Inst Inorgan Chem, Fac Math & Nat Sci, Dept Chem, D-50939 Cologne, Germany

[3] Islamic Azad Univ, Shiraz Branch, Dept Chem, Shiraz 7199337635, Iran

来源：

ORGANOMETALLICS | 2023年 / 42卷 / 06期

关键词：

H BOND ACTIVATION; REDUCTIVE ELIMINATION; OXIDATIVE ADDITION; C-C; NITROGEN LIGANDS; ALKYL-HALIDES; I BOND; COMPLEXES; PLATINUM(II); PALLADIUM;

D O I：

10.1021/acs.organomet.3c00050

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

C???C cross-coupling versus homo-coupling from the Pt(IV) complex [Pt(pbt)Br(CH2Ph)(Me)2], 2a (pbt = 2-(2-pyridyl)benzothiazole), was studied experimentally and through density functional theory calculations. The calculations show that from the three competitive C???C reductive eliminations, (A) Me???Me homo-coupling, (B) benzyl???Me cross-coupling (Me trans to Npy), and (C) benzyl???Me cross-coupling (Me trans to Nbz), the Me???Me homo-coupling reaction is preferred over the other two due to the lower energy barrier of the Me???Me vs the benzyl???Me bond formation. The reaction is initiated by a dissociation of the Br??? ligand followed by Me???Me homo-coupling from the resulting five-coordinate intermediate. Experimentally, complex 2a undergoes reductive elimination in toluene at 70 ??C producing ethane and the Pt(II) complex [Pt(pbt)Br(CH2Ph)] 3a in over 99% yield, fully in line with the calculations. 1H195Pt HMBC experiments allowed studying even sub-% products in this study.

引用

页码：486 / 494

页数：9

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