Palladium iminophosphorane complexes: the pre-cursors to the missing link in triphenylphosphane chalcogenide metallacycles. Issue 44 (25th October 2018)

• Record Type: Journal Article
• Authors: Fernández-Figueiras, Adolfo; Lucio-Martínez, Fátima; Munín-Cruz, Paula; Polo-Ces, Paula; Reigosa, Francisco; Adams, Harry; Pereira, M. Teresa; Vila, José M.
• Is Part Of: Dalton transactions. Volume 47:Issue 44(2018)
• Page Start: 15801
• Page End: 15807
• Publication Date: 2018-10-25
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt03062f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A dinuclear iminophosphorane palladacycle produces the missing link in the triphenylphosphane chalcogenide series of metallacycles. Abstract : Herein we report on the synthesis, characterization and the ensuing chemistry of iminophosphorane palladacycles. Treatment of Ph3 PN-(2-OHC6 H4 ), 1, with sodium tetrachloropalladate gives2 with the ligand as terdentate [ C, N, O ] allowing for only one μ-Cl ligand bonding the metal centers, resulting in a dinuclear complex. Treatment of2 with PPh3 gives the mononuclear complex3, whereas the reaction of2 with diphosphanes Ph2 P(CH2 ) n PPh2 in 1 : 2 ratio gives mixtures of4 and5 ( n = 2) and6 and7 ( n = 3). From them, the mononuclear complexes4 and6, and the dinuclear compounds, 5 and7, were obtained with the parent ligand as bidentate [ C, N ]. The former two are of zwitterionic nature void of any counterion, with the phosphane ligand in the chelating mode. In a remarkable case of chemical serendipity, a solution of2 left to stand produced crystals of complex8 : this is the missing link in the series of triphenylphosphane chalcogenide metallacycles. The experiment is repeatable; however, direct metallation of triphenylphosphane oxide was not possible.