620987-70-4Relevant academic research and scientific papers
A structure-activity relationship for pincer palladium(II) complexes - Influence of ring-size of metallacycles on the activity in allylic alkylation
Wang, Zhaohui,Eberhard, Michael R.,Jensen, Craig M.,Matsukawa, Shiro,Yamamoto, Yohsuke
, p. 189 - 195 (2003)
A series of new palladium(II) complexes derived from the well-known pincer complex [PdCl{(C6H3)(OPi Pr2)2-2,6}] were synthesised: [PdX{(C6 H3)(OPiPr2)2-2,6}] (X = Br-, I-, OAc-, OTf-). A novel PCP′ pincer ligand 1-(iPr2 PO)-3-(iPr2POCH2)(C6 H4) was prepared and complexed to palladium(II) to give [PdX{(C6H3)(OPiPr2)-2- (CH2OPiPr2)-6}] (X=Cl-, I-, OAc-, OTf-, BF4 -). The X-ray structure of [PdCl{(C6H3) (OPiPr2)-2-(CH2OPi Pr2)-6}] was solved and is discussed. These complexes were applied to the catalytic reaction of cinnamyl acetate with sodium dimethyl malonate in order to evaluate the influence of the ligand structure and co-ordinating or non-co-ordinating anions on the regioselectivity. A detailed analysis shows that palladium(II) complexes of the unsymmetrical PCP′ bis(phosphinito) ligand are much more active when compared to related complexes of the symmetrical PCP bis(phosphinito) ligand. The origin of this difference in activity is discussed.
Synthesis of unsymmetrical 5,6-POCOP′-type pincer complexes of nickel(II): Impact of nickelacycle size on structures and spectroscopic properties
Salah, Abderrahmen,Corpet, Martin,Ul-Hassan Khan, Najm,Zargarian, Davit,Spasyuk, Denis M.
, p. 6649 - 6658 (2015/08/06)
This report describes the synthesis and characterization of a family of unsymmetrical pincer complexes of nickel(ii), featuring both 5- and 6-membered nickelacycles. The room temperature reaction of NiBr2(NCCH3)x with bis(phosphinite) ligand, 1-(i-Pr2PO),3-(i-Pr2POCH2)-C6H4 (POCHOP′), results in direct nickelation at the 2-position of the aromatic ring to give (5,6-POCOP′)NiBr (5,6-POCOP′ = κP,κC,κP′-2-(i-Pr2PO),6-(i-Pr2POCH2)-C6H3). This complex undergoes salt metathesis reactions with M′X to give the corresponding charge neutral derivatives, (5,6-POCOP′)NiX (X = OSO2CF3, OSO2(4-CH3-C6H4), CH3, and CCCH3), whereas the abstraction of bromide by AgBPh4 in acetonitrile gave the cationic derivative, [(5,6-POCOP′)Ni(NCCH3)][BPh4]. The new complexes have been characterized by multinuclear NMR spectroscopy and X-ray diffraction studies. The reactivities of the new complexes (5,6-POCOP′)NiX (X = Br, OSO2CF3) have been explored briefly to establish the nucleophilicity of the X ligand and the substitutional lability of the phosphinite moiety in the 6-membered cycle.
A series of pincer-ligated rhodium complexes as catalysts for the dimerization of terminal alkynes
Pell, Christopher J.,Ozerov, Oleg V.
, p. 3470 - 3480 (2015/02/19)
A series of pincer complexes of Rh has been prepared and tested as catalysts for the dimerization of terminal alkynes. The pincers included aryl/bis(phosphinite) POCOP, aryl/bis(phosphine) PCP, and diarylamido/bis(phosphine) PNP ligands. RhI co
