Organometallic Nucleophiles and Pd: What Makes ZnMe2 Different? Is Au Like Zn?Click to copy article linkArticle link copied!
Abstract
The cis/trans isomerization of [PdMeAr(PR3)2] complexes (Ar = C6F5, C6F3Cl2) can take place spontaneously (via dissociation and topomerization, studied experimentally) or be catalyzed by ZnMe2. The latter mechanism, studied by DFT methods, involves methyl exchange between Pd and Zn. The study of this catalyzed isomerization shows that, in contrast with the typical acidic behavior of Zn in ZnMeCl, Zn in ZnMe2 (or, more exactly, the ZnMe bond) behaves as a strong basic center, able to attack the relatively high in energy acceptor orbital at Pd in fairly electron rich Pd complexes such as [PdArMeL2] or [PdMe2L2]. This makes the two reagents very different in Negishi couplings. The catalyzed isomerization occurs via transmetalation; thus, both processes are connected. A comparison of the Pd/Zn intermediates and transition states with those found previously for Pd/Au transmetalations reveals very similar structures with intermetallic distances in the order of or noticeably shorter than the sum of the vdW radii, regardless of the nature of the metal (metallophilic Au or nonmetallophillic Zn). These short distances are associated with the involvement of the metals in 3c2e electron deficient bonds during R group transmetalation. In this respect, there is a remarkable similarity to the structurally known behavior of main-group electron-deficient compounds, which supports a unified view of the transmetalation processes.
Cited By
This article is cited by 24 publications.
- Marina Pérez-Jiménez, Jesús Campos, Jesús Jover, Santiago Álvarez, Ernesto Carmona. Coordination of E–C Bonds (E = Zn, Mg, Al) and the Zn–H Bonds of (C5Me5)ZnH and (C5Me5)ZnZnH across a Quadruply Bonded Dimolybdenum Dihydride Complex. Organometallics 2022, 41
(22)
, 3225-3236. https://doi.org/10.1021/acs.organomet.2c00216
- Raphael J. Oeschger, Raphael Bissig, Peter Chen. Model Compounds for Intermediates and Transition States in Sonogashira and Negishi Coupling: d8–d10 Bonds in Large Heterobimetallic Complexes Are Weaker than Computational Chemistry Predicts. Journal of the American Chemical Society 2022, 144
(23)
, 10330-10343. https://doi.org/10.1021/jacs.2c01641
- Nereida Hidalgo, Carlos Romero-Pérez, Celia Maya, Israel Fernández, Jesús Campos. Reactivity of [Pt(PtBu3)2] with Zinc(I/II) Compounds: Bimetallic Adducts, Zn–Zn Bond Cleavage, and Cooperative Reactivity. Organometallics 2021, 40
(8)
, 1113-1119. https://doi.org/10.1021/acs.organomet.1c00088
- Pedro Villar, Mónica H. Pérez-Temprano, Juan A. Casares, Rosana Álvarez, Pablo Espinet. Experimental and DFT Study of the [AuAr(AsPh3)]-Catalyzed cis/trans Isomerization of [PdAr2(AsPh3)2] (Ar = C6F5 or C6Cl2F3): Alternative Mechanisms and Its Switch upon Pt for Pd Substitution. Organometallics 2020, 39
(12)
, 2295-2303. https://doi.org/10.1021/acs.organomet.0c00245
- Mikhail V. Polynski, Valentine P. Ananikov. Modeling Key Pathways Proposed for the Formation and Evolution of “Cocktail”-Type Systems in Pd-Catalyzed Reactions Involving ArX Reagents. ACS Catalysis 2019, 9
(5)
, 3991-4005. https://doi.org/10.1021/acscatal.9b00207
- Sheida Rajabi, Sirous Jamali, Soroosh Naseri, Ali Jamjah, Reza Kia, Hamidreza Samouei, Piero Mastrorilli, Hamid R. Shahsavari, Paul R. Raithby. Pt–M (M = Au and Tl) Dative Bonds Using Bis(cyclometalated)platinum(II) Complexes. Organometallics 2019, 38
(8)
, 1709-1720. https://doi.org/10.1021/acs.organomet.8b00907
- María Pérez-Iglesias, Olmo Lozano-Lavilla, Juan A. Casares. [Cu(C6Cl2F3)(tht)]4: An Extremely Efficient Catalyst for the Aryl Scrambling between Palladium Complexes. Organometallics 2019, 38
(4)
, 739-742. https://doi.org/10.1021/acs.organomet.8b00885
- Eno Paenurk, Renana Gershoni-Poranne, and Peter Chen . Trends in Metallophilic Bonding in Pd–Zn and Pd–Cu Complexes. Organometallics 2017, 36
(24)
, 4854-4863. https://doi.org/10.1021/acs.organomet.7b00748
- Hong Zheng, Kazuhiko Semba, Yoshiaki Nakao, and Shigeyoshi Sakaki . How to Control Inversion vs Retention Transmetalation between PdII–Phenyl and CuI–Alkyl Complexes: Theoretical Insight. Journal of the American Chemical Society 2017, 139
(40)
, 14065-14076. https://doi.org/10.1021/jacs.7b04383
- Yousef Khaledifard, Bahare Nasiri, Saeid A. Javidy, Atena Vaziri Sereshk, Brian F. Yates, and Alireza Ariafard . Phosphine-Scavenging Role of Gold(I) Complexes from Pd(PtBu3)2 in the Bimetallic Catalysis of Carbostannylation of Alkynes. Organometallics 2017, 36
(10)
, 2014-2019. https://doi.org/10.1021/acs.organomet.7b00237
- Juan del Pozo, María Pérez-Iglesias, Rosana Álvarez, Agustí Lledós, Juan A. Casares, Pablo Espinet. Speciation of ZnMe2, ZnMeCl, and ZnCl2 in Tetrahydrofuran (THF), and Its Influence on Mechanism Calculations of Catalytic Processes. ACS Catalysis 2017, 7
(5)
, 3575-3583. https://doi.org/10.1021/acscatal.6b03636
- Raphael J. Oeschger and Peter Chen . Structure and Gas-Phase Thermochemistry of a Pd/Cu Complex: Studies on a Model for Transmetalation Transition States. Journal of the American Chemical Society 2017, 139
(3)
, 1069-1072. https://doi.org/10.1021/jacs.6b12152
- Juan del Pozo, Gorka Salas, Rosana Álvarez, Juan A. Casares, and Pablo Espinet . The Negishi Catalysis: Full Study of the Complications in the Transmetalation Step and Consequences for the Coupling Products. Organometallics 2016, 35
(20)
, 3604-3611. https://doi.org/10.1021/acs.organomet.6b00660
- R. Govindarajan, Pavan K. Vardhanapu, Robert R. Fayzullin, Eugene Khaskin, Julia R. Khusnutdinova. Facile methyl group transfer from Pt
II
to gallium and indium. Chemical Communications 2024, 60
(56)
, 7216-7219. https://doi.org/10.1039/D4CC02112F
- Zeinab Ahmadvand, Mehdi Bayat. Negishi or Suzuki–Miyaura Pd-Catalyzed Cross-Coupling Reaction: Which Reaction Mechanism is Ahead for the Formation of Well-Known Anticancer Drug Combretastatin A-4 Analogue?. Journal of Computational Biophysics and Chemistry 2023, 22
(04)
, 423-438. https://doi.org/10.1142/S2737416523500175
- Ramadoss Govindarajan, Shubham Deolka, Eugene Khaskin, Robert R. Fayzullin, Shrinwantu Pal, Serhii Vasylevskyi, Julia R. Khusnutdinova. H
2
, B−H, and Si−H Bond Activation and Facile Protonolysis Driven by Pt‐Base Metal Cooperation. Chemistry – A European Journal 2022, 28
(44)
https://doi.org/10.1002/chem.202201639
- Stéphanie Halbert, Hélène Gérard. Cu(I)-Assisted Addition of Li- or Zn-Organometallics to Carbonyl Compounds: Learning from Analogies and Differences Between Intermediates and Transition States. Topics in Catalysis 2022, 65
(1-4)
, 481-492. https://doi.org/10.1007/s11244-021-01551-9
- Desiré Carrasco, Juan A. Casares. Experimental study of the [ZnCl2(THF)2] catalyzed cis/trans-isomerization of [Pd(C6Cl2F3)Me(PPh3)2] and of the transmetalation of trans-[PdCl(C6Cl2F3)(PPh3)2] with [ZnMeCl(THF)2]. Inorganica Chimica Acta 2021, 517 , 120206. https://doi.org/10.1016/j.ica.2020.120206
- Mikhail V. Polynski, Evgeny A. Pidko. Intermetallic species in the Negishi coupling and their involvement in inhibition pathways. Catalysis Science & Technology 2019, 9
(17)
, 4561-4572. https://doi.org/10.1039/C9CY00752K
- Jesús Campos, Ainara Nova, Eugene L. Kolychev, Simon Aldridge. A Combined Experimental/Computational Study of the Mechanism of a Palladium‐Catalyzed Bora‐Negishi Reaction. Chemistry – A European Journal 2017, 23
(51)
, 12655-12667. https://doi.org/10.1002/chem.201702703
- Jesús Campos, Joaquín López‐Serrano, Riccardo Peloso, Ernesto Carmona. Methyl Complexes of the Transition Metals. Chemistry – A European Journal 2016, 22
(19)
, 6432-6457. https://doi.org/10.1002/chem.201504483
- D. Carrasco, M. García-Melchor, J. A. Casares, P. Espinet. Dramatic mechanistic switch in Sn/Au
I
group exchanges: transmetalation vs. oxidative addition. Chemical Communications 2016, 52
(23)
, 4305-4308. https://doi.org/10.1039/C5CC10496C
- Roberto Molteni, Rüdiger Bertermann, Katharina Edkins, Andreas Steffen. An unexpected transmetalation intermediate: isolation and structural characterization of a solely CH
3
bridged di-copper(
i
) complex. Chemical Communications 2016, 52
(28)
, 5019-5022. https://doi.org/10.1039/C6CC01510G
- Allegra L. Liberman-Martin, Daniel S. Levine, Micah S. Ziegler, Robert G. Bergman, T. Don Tilley. Lewis acid–base interactions between platinum(
ii
) diaryl complexes and bis(perfluorophenyl)zinc: strongly accelerated reductive elimination induced by a Z-type ligand. Chemical Communications 2016, 52
(43)
, 7039-7042. https://doi.org/10.1039/C6CC02433E
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.