Are Sc—C and Sc—P Bonds Reactive in Scandium Phosphinoalkylidene Complex? Insights on a Versatile Reactivity1. Issue 10 (27th July 2018)

• Record Type: Journal Article
• Authors: Mao, Weiqing; Xiang, Li; Lamsfus, Carlos Alvarez; Maron, Laurent; Leng, Xuebing; Chen, Yaofeng
• Is Part Of: Chinese journal of chemistry. Volume 36:Issue 10(2018)
• Page Start: 904
• Page End: 908
• Publication Date: 2018-07-27
• Subjects: alkylidene -- density functional calculations -- multiple bonds -- phosphorus -- scandium; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cjoc.201800253
• Languages: English
• ISSNs: 1001-604X

Abstract

Abstract : The peculiar electronic structure of scandium phosphinoalkylidene complex [LSc{C(SiMe3 )PPh2 }THF] (L=[MeC(NDIPP)CHC(NDIPP)Me] − ), DIPP=2, 6‐( i Pr)2 C6 H3 ) leads to an interesting versatile reactivity, which is demonstrated both experimentally and computationally. Abstract: The peculiar electronic structure of scandium phosphinoalkylidene complex [LSc{C(SiMe3 )PPh2 }THF] (L=[MeC(NDIPP)CHC(NDIPP)Me] − ), DIPP=2, 6‐( i Pr)2 C6 H3 ) leads to an interesting versatile reactivity, which is demonstrated both experimentally and computationally. The complex undergoes [2+2] cycloaddition reactions with alkynes, and easily activates various X—O bonds such as C—O of propylene oxide, N—O of 3, 5‐dimethylisoxazole, B—O of pinacolborane and Si—O of triethoxysilane. These reactions occur on the Sc—C bond of the phosphinoalkylidene complex. Interestingly, the Sc—P bond can also be activated as the presence of a Sc—C—P three center π interaction in the complex allows performing C—F activation of 2, 6‐difluoropyridine and 1, 2 addition with imine or ketone. The complex also reacts with metal complexes, [(COD)RhCl]2 and (Ph3 P)AuCl, to form structural intriguing heterobimetallic complexes.