التفاصيل البيبلوغرافية
| العنوان: |
Bridging the Gap from Mononuclear Pd II Precatalysts to Pd Nanoparticles: Identification of Intermediate Linear [Pd 3 (XPh 3 ) 4 ] 2+ Clusters as Catalytic Species for Suzuki–Miyaura Couplings (X = P, As) |
| المؤلفون: |
Kate M. Appleby (4863124), Evans Dzotsi (11592085), Neil W. J. Scott (11592088), Guan Dexin (11592091), Neda Jeddi (1713103), Adrian C. Whitwood (1305204), Natalie E. Pridmore (1364133), Sam Hart (50699), Simon B. Duckett (1277202), Ian J. S. Fairlamb (8653962) |
| سنة النشر: |
1753 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Cancer, Environmental Sciences not elsewhere classified, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, similarly catalytically active, brominated heterocyclic 2, band uv irradiation, high activity seen, ii , 2 +, 3 , mononuclear pd catalysts, seen previously, mononuclear pd, defined mononuclear, typical c2, thermal isomer, site selectivity, remarkable change, pd nanoparticles, give styrene, findings link, cluster isomerizes, cluster enables, catalyzed hydrogenation, catalytic role, bromide site, atypical c4 |
| الوصف: |
Tripalladium clusters of the type [Pd 3 (PPh 3 ) 4 ] 2+ , wherein three linearly connected Pd atoms are stabilized by phosphine and arsine ligands, have been detected and isolated as intermediates during the reduction of well-defined mononuclear [Pd(OTf) 2 (XPh 3 ) 2 ] (X = P and X = As, respectively) to Pd nanoparticles (PdNPs). The isolated [Pd 3 (PPh 3 ) 4 ] 2+ cluster isomerizes on broad-band UV irradiation to form an unexpected photoisomer, produced by a remarkable change in conformation at one of the bridging PPh 3 ligands. A catalytic role for these [Pd 3 (XPh 3 ) 4 ] 2+ species is exemplified in Suzuki–Miyaura cross-coupling (SMCC) reactions, with high activity seen in the arylation of a brominated heterocyclic 2-pyrone. Use of the [Pd 3 (PPh 3 ) 4 ] 2+ cluster enables a switch in site selectivity for SMCC reactions involving 2,4-dibromopyridine from the typical C2-bromide site (seen previously for mononuclear Pd catalysts) to the atypical C4-bromide site, thereby mirroring recently reported cyclic Pd 3 clusters and PdNPs. We have further determined that the thermal isomer and photoisomer of [Pd 3 (PPh 3 ) 4 ] 2+ are similarly catalytically active in the Pd-catalyzed hydrogenation of phenylacetylene to give styrene. Our findings link the evolution of mononuclear Pd(II) salts to PdNPs via the intermediacy of linear [Pd 3 (XPh 3 ) 4 ] 2+ clusters. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Bridging_the_Gap_from_Mononuclear_Pd_sup_II_sup_Precatalysts_to_Pd_Nanoparticles_Identification_of_Intermediate_Linear_Pd_sub_3_sub_XPh_sub_3_sub_sub_4_sub_sup_2_sup_Clusters_as_Catalytic_Species_for_Suzuki_Miyaura_Couplings_X_P_As_/16847629 |
| DOI: |
10.1021/acs.organomet.1c00452.s001 |
| الاتاحة: |
https://doi.org/10.1021/acs.organomet.1c00452.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.4A30DFC |
| قاعدة البيانات: |
BASE |