Well-defined BisMETAMORPhos PdI-PdI complex: synthesis, structural characterization, and reactivity
Autor: | Oldenhof, Sander, Lutz, Martin, De Bruin, Bas, Van Der Vlugt, Jarl Ivar, Reek, Joost N H, Sub Crystal and Structural Chemistry, Crystal and Structural Chemistry |
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Přispěvatelé: | Homogeneous and Supramolecular Catalysis (HIMS, FNWI), Sub Crystal and Structural Chemistry, Crystal and Structural Chemistry |
Jazyk: | angličtina |
Rok vydání: | 2014 |
Předmět: | |
Zdroj: | Organometallics, 33(24), 7293. American Chemical Society Organometallics, 33(24), 7293-7298. American Chemical Society |
ISSN: | 0276-7333 |
Popis: | The formation of a bisMETAMORPhos PN-bridged dimeric PdI complex (3) from ligand 1 and Pd(dba)2 is described. The addn. of 1 to Pd(dba)2 initially leads to the formation of Pd0 complex 2, which has a highly distorted tetrahedral environment and binds two neutral ligands 1. Complex 2 converts to {PdI}2 complex 3 upon heating. Complex 3 consists of a completely flat Pd-Pd core, with a Pd-Pd bond length of 2.6199(4) Å, and the Pd centers display a highly distorted square planar coordination environment. The formation of complex 3 from 2 is suggested to proceed via an in situ comproportionation pathway. Initial decoordination of one ligand from 2 followed by oxidative addn. of one neutral coordinated ligand arm leads to a 1-PdIIH complex. Insertion of free dba into the Pd-H bond generates a 1-PdIIdba complex that releases 1,5-diphenylpent-1-en-3-one via intra- or intermol. protonolysis. Concomitantly, comproportionation with 1-Pd0 yields 3. Complex 3 was found to function as a precatalyst in the Suzuki-Miyaura cross-coupling of p-chloroacetophenone with good conversions. |
Databáze: | OpenAIRE |
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