Synthesis, Characterization, and Reactivity of Cationic Palladium(II) and Platinum(II) Iodo Complexes Containing a Linear or a Tripodal Aminophosphine. The X-Ray Crystal Structures of [Pd{HN(CH2CH2PPh2)2}I]I and [Pd3{N(CH2CH2PPh2}3)2I4]I2Dedicated to Professor Joachim Strähle on the Occasion of his 65th Birthday

Abstract

The complexes [M(PNHP)I]I (PNHP ϭ bis[2-(diphenylphosphino)ethyl]amine; M ϭ Pd (1), Pt (2)) and [M(NP 3 )I]I (NP 3 ϭ tris[2-(diphenylphosphino)ethyl]amine; M ϭ Pd (3), Pt (4)) were prepared by interaction of the appropriate aminophosphine in CH 2 Cl 2 with aqueous solutions containing [MCl 4 ] 2Ϫ salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt 2 (PNHP) 3 ]I 4 (2a) and [Pd 3 (NP 3 ) 2 I 4 ]I 2 (3a) in the presence of coordinating solvents such as the mixture CD 3 OD/D 2 O/ DMSO-d 6 and CH 2 Cl 2 /CH 3 OH, respectively. Complex 1 consists of distorted square-planar cations [Pd(PNHP)I] ϩ and iodide anions able to establish short N-H···I interactions of 2.850 Å . The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square-planar Pd II atoms, PdNP 2 I and trans-PdP 2 I 2 , NP 3 acting as tridentate chelating and bridging ligand, respectively. On the basis of 31 P { 1 H} NMR data it has been shown that each distorted square-planar Pt(II) centre of 2a contains one PNHP acting as tri-

Electrocatalytic property, anticancer activity, and density functional theory calculation of [NiCl(P^N^P)]Cl.EtOH

“…In addition, two signals were observed at 2.8 and 2.4 ppm assigned to the methylene groups. In the 31 P NMR spectrum of the ligand showed a major signal can be seen at −21.5 ppm, which is consistent with reported values [62,66,67] and a minor one at 34.5 ppm for the oxidized product. [62] The 1 H, 13 C, and 31 P NMR of [NiCl(P^N^P)]Cl are shown in Figures S2-S4.…”

“…In contrast to the usual synthetic methods, which are based on time‐consuming and costly amine protection (Scheme 3a), this study avoids this by using LiPPh 2 which has low basicity and high nucleophilicity thereby preventing the aziridine formation (Scheme 3). [ 38,65,66 ]…”

“…In contrast to the usual synthetic methods, which are based on time-consuming and costly amine protection (Scheme 3a), this study avoids this by using LiPPh 2 which has low basicity and high nucleophilicity thereby preventing the aziridine formation (Scheme 3). [38,65,66] The P^N^P ligand was then characterized by 1 H NMR, 31 P NMR, FT-IR, UV-vis, and single-crystal X-ray diffraction. The calculated and experimental FT-IR spectra of the Ni complex and the ligand are shown in Figure S1.…”

Ring-opening reactions induced by gold(i) of five- and four-coordinate palladium(ii) and platinum(ii) complexes containing tripodal or linear polyphosphines

“…The reaction of the ligands NP 3 , PP 3 or P 4 in CH 2 Cl 2 or CHCl 3 with aqueous or methanolic solutions of the appropriate Pd(II) or Pt(II) precursor in 1 : 1 molar ratio leads to the synthesis of the mononuclear complexes [M(L)X]X (1-9) and [Pt(P 4 )](BPh 4 ) 2 (10). While the interaction between [Pd(NP 3 )X]X (1-3) (MeOH, CH 2 Cl 2 ) and Au(tdg)X (MeOH, Et 2 O) or commercial AuI only affords the heterobimetallic compounds PdAu(NP 3 )X 3 (11)(12)(13), complexes [M(PP 3 )X]X (4-9) (CHCl 3 ) react with gold(I) in 1 : 1 and 1 : 2 stoichiometric ratios achieving the mixed metal species [MAu(PP 3 )X 2 ]X (14)(15)(16)(17)(18)(19) and MAu 2 (PP 3 )X 4 [M = Pd (20)(21)(22), Pt (23)]. Another procedure to obtain complexes 20-23 consists of the addition of one equivalent of Au(I) to compounds 14-17.…”

“…(NP 3 = tris[2-(diphenylphosphino)ethyl]amine) 15 and [Pt(NP 3 )I]I 16 giving ionic and neutral squareplanar and ionic square-pyramidal complexes containing dangling arm phosphine oxide groups. Likewise, the phosphine PNHP (bis[2-(diphenylphosphino)ethyl]amine) induces a ring-opening reaction in [Pd(PNHP)Cl]Cl to give a five-coordinate complex [Pd(PNHP) 2 ]Cl 2 17 and the interaction between Au(I) and [M(triphos)X]X 18,19 allows to obtain neutral heterobimetallic compounds MAu(triphos)X 3 (M = Pd, Pt, X = Cl, Br; M = Pd, X = I) with four-and two-coordinate M(II) and Au(I) centres, respectively.…”