Chloropalladated tetranuclear and copper(I) complexes of propargylamines [RC≡CCH2NC4H8NCH2C≡CR]

Publication date: Available online 10 July 2019Source: Journal of Organometallic ChemistryAuthor(s): Vitthalrao S. Kashid, Basvaraj S. Kote, S. Balakrishna MaravanjiAbstractThe reactions of propargylamines 1,4-bis(3-phenylprop-2-yn-1-yl)piperazine (1) and 1,4-bis(3-(trimethylsilyl)prop-2-yn-1-yl)piperazine (2) with PdCl2 and CuI is described. 1,4-Bis(3-phenylprop-2-yn-1-yl)piperazine reacts with one equivalent of PdCl2 to afford κ2-N,N-coordinated complexes [PdCl2{Me3SiC≡CCH2NC4H8NCH2C≡CSiMe3-κ2-N,N] (3) and [PdCl2{Me3SiC≡CCH2NC4H8NCH2C≡CSiMe3}-κ2-N,N] (4). The reactions of 1 and 2 with two equivalents of PdCl2 yielded rare chloropalladated tetranuclear complexes [Pd4(μ-Cl4)Cl4(PhC≡CCH2NC4H8NCH2C≡CPh)2] (5) and [Pd4(μ-Cl4)Cl4(Me3SiC≡NC4H8NCH2C≡C SiMe3)2] (6), respectively, resulting from the trans nucleophilic addition of chloride ion onto the electrophilic C≡C bond. The reactions of 1 and 2 with two equivalents of CuI produced 2-D coordination polymers [{Cu2(μ-I)}2(PhC≡C–CH2NC4H8NCH2C≡CPh)]n (7) and [{Cu2(μ-I)}2(Me3SiC≡CCH2NC4H8NCH2C≡CSiMe3)]n (8), respectively. Similar reactions in 1:1 M ratios produced dimeric complexes [Cu2(μ-I)2(PhC≡CCH2NC4H8NCH2C≡CPh)2] (9) and [Cu2(μ-I)2(Me3SiC≡CCH2NC4H8NCH2C≡CSiMe3)2] (10), respectively. The structures of compounds 3, 5 and 7 have been established by single crystal X-ray analysis.Graphical abstract

Source: Journal of Organometallic Chemistry - July 12, 2019 Category: Chemistry Source Type: research