A Low-coordinate Platinum(0)-germylene for E-H Bond Activation and Catalytic Hydrodehalogenation

Overview

Journal Nat Commun

Specialty Biology

Date 2024 Nov 7

PMID 39511155

Authors

Sonia Bajo

Enrique Soto

Marta Fernandez-Buenestado

Joaquin Lopez-Serrano

Jesus Campos

Affiliations

Soon will be listed here.

Abstract

Pairing transition metals and heavier tetrylenes (Si, Ge, Sn, Pb) holds great potential for cooperative bond activation and catalysis. In this work, we investigate the reactivity of a low-coordinate Pt(0)/Ge(II) system that emerges from the reaction between the monoligated platinum(0) precursor [(PMeAr)Pt(olefin)] with germylene dimer [ArGeCl] (where Ar = CH-2,6-(CH-2,6-Pr)). The resulting complex reveals ability for cooperative bond activation. Stoichiometric reactions with dihydrogen, water, methanol, ammonia and alkynes unveil the formation of Pt(II)-germyl compounds, characterized by distinct isomeric forms, whose flexibility derives from the particularly low-coordination. We explore its catalytic potential in the hydrodehalogenation of aliphatic, aromatic and main-group halides under dihydrogen atmosphere using both thermal and photochemical conditions, demonstrating promising conversions even for more challenging alkyl chlorides.

References

Hidalgo N, Moreno J, Perez-Jimenez M, Maya C, Lopez-Serrano J, Campos J . Tuning Activity and Selectivity during Alkyne Activation by Gold(I)/Platinum(0) Frustrated Lewis Pairs. Organometallics. 2020; 39(13):2534-2544. PMC: 7707620. DOI: 10.1021/acs.organomet.0c00330. View

Butler M, Crimmin M . Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals. Chem Commun (Camb). 2017; 53(8):1348-1365. PMC: 5777540. DOI: 10.1039/c6cc05702k. View

Claros M, Ungeheuer F, Franco F, Martin-Diaconescu V, Casitas A, Lloret-Fillol J . Reductive Cyclization of Unactivated Alkyl Chlorides with Tethered Alkenes under Visible-Light Photoredox Catalysis. Angew Chem Int Ed Engl. 2019; 58(15):4869-4874. PMC: 6519206. DOI: 10.1002/anie.201812702. View

Alonso F, Beletskaya I, Yus M . Metal-mediated reductive hydrodehalogenation of organic halides. Chem Rev. 2002; 102(11):4009-91. DOI: 10.1021/cr0102967. View

Hopkinson M, Richter C, Schedler M, Glorius F . An overview of N-heterocyclic carbenes. Nature. 2014; 510(7506):485-96. DOI: 10.1038/nature13384. View

Hadlington T, Szilvasi T, Driess M . Versatile Tautomerization of EH-Substituted Silylenes (E = N, P, As) in the Coordination Sphere of Nickel. J Am Chem Soc. 2019; 141(7):3304-3314. DOI: 10.1021/jacs.9b00159. View

Lipke M, Liberman-Martin A, Don Tilley T . Significant Cooperativity Between Ruthenium and Silicon in Catalytic Transformations of an Isocyanide. J Am Chem Soc. 2016; 138(30):9704-13. DOI: 10.1021/jacs.6b05736. View

Zhao J, Goldman A, Hartwig J . Oxidative addition of ammonia to form a stable monomeric amido hydride complex. Science. 2005; 307(5712):1080-2. DOI: 10.1126/science.1109389. View

Pu L, Phillips A, Richards A, Stender M, Simons R, Olmstead M . Germanium and tin analogues of alkynes and their reduction products. J Am Chem Soc. 2003; 125(38):11626-36. DOI: 10.1021/ja035711m. View

10.

Sahoo B, Surkus A, Pohl M, Radnik J, Schneider M, Bachmann S . A Biomass-Derived Non-Noble Cobalt Catalyst for Selective Hydrodehalogenation of Alkyl and (Hetero)Aryl Halides. Angew Chem Int Ed Engl. 2017; 56(37):11242-11247. DOI: 10.1002/anie.201702478. View

11.

Bajo S, Theulier C, Campos J . Mechanistic Investigations on Hydrogenation, Isomerization and Hydrosilylation Reactions Mediated by a Germyl-Rhodium System. ChemCatChem. 2022; 14(15):e202200157. PMC: 9401076. DOI: 10.1002/cctc.202200157. View

12.

Keil P, Szilvasi T, Hadlington T . Reversible metathesis of ammonia in an acyclic germylene-Ni complex. Chem Sci. 2021; 12(15):5582-5590. PMC: 8179610. DOI: 10.1039/d1sc00450f. View

13.

Hinchley S, Morrison C, Rankin D, Macdonald C, Wiacek R, Voigt A . Spontaneous generation of stable pnictinyl radicals from "jack-in-the-box" dipnictines: a solid-state, gas-phase, and theoretical investigation of the origins of steric stabilization. J Am Chem Soc. 2001; 123(37):9045-53. DOI: 10.1021/ja010615b. View

14.

Chatterjee I, Porwal D, Oestreich M . B(C F ) -Catalyzed Chemoselective Defunctionalization of Ether-Containing Primary Alkyl Tosylates with Hydrosilanes. Angew Chem Int Ed Engl. 2017; 56(12):3389-3391. DOI: 10.1002/anie.201611813. View

15.

Maity A, Teets T . Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes. Chem Rev. 2016; 116(15):8873-911. DOI: 10.1021/acs.chemrev.6b00034. View

16.

Sugahara T, Guo J, Hashizume D, Sasamori T, Tokitoh N . Reversible Isomerizations between 1,4-Digermabenzenes and 1,4-Digerma-Dewar-benzenes: Air-Stable Activators for Small Molecules. J Am Chem Soc. 2019; 141(6):2263-2267. DOI: 10.1021/jacs.9b00129. View

17.

Asay M, Jones C, Driess M . N-heterocyclic carbene analogues with low-valent group 13 and group 14 elements: syntheses, structures, and reactivities of a new generation of multitalented ligands. Chem Rev. 2010; 111(2):354-96. DOI: 10.1021/cr100216y. View

18.

Mitoraj M, Michalak A, Ziegler T . A Combined Charge and Energy Decomposition Scheme for Bond Analysis. J Chem Theory Comput. 2015; 5(4):962-75. DOI: 10.1021/ct800503d. View

19.

Ortega-Moreno L, Peloso R, Maya C, Suarez A, Carmona E . Platinum(0) olefin complexes of a bulky terphenylphosphine ligand. Synthetic, structural and reactivity studies. Chem Commun (Camb). 2015; 51(95):17008-11. DOI: 10.1039/c5cc07308a. View

20.

Charman R, Evans N, English L, Neale S, Vasko P, Mahon M . The structures and reactivity of NHC-supported copper(i) triphenylgermyls. Chem Sci. 2024; 15(2):584-593. PMC: 10763552. DOI: 10.1039/d3sc05862j. View