Macrocyclic Platinum(II) Complexes with a Bifunctional Diphosphine Ligand. Issue 34 (13th November 2015)

• Record Type: Journal Article
• Authors: Pascui, Andrea E.; van Rees, Karlotta; Zant, Dirk W.; Broere, Daniël L. J.; Siegler, Maxime A.; van der Vlugt, Jarl Ivar
• Is Part Of: European journal of inorganic chemistry. Issue 34(2015)
• Page Start: 5687
• Page End: 5693
• Publication Date: 2015-11-13
• Subjects: N, P ligands -- Metallacycles -- Platinum -- Macrocyclic ligands -- Ligand design; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501055
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The preparation and coordination chemistry of a ditopic ligand scaffold (1 H2 ), containing both a phosphorus‐donor ( P ) and a nitrogen‐donor ( N ) binding pocket, is reported. The ligand was synthesized by reductive amination from 3‐(diphenylphosphino)benzaldehyde and N ‐(2‐aminophenyl)‐ N ‐methylbenzene‐1, 2‐diamine. Selective coordination in the P ‐pocket was achieved for Pt II, with careful control over the reaction conditions and precursor materials providing access to either the thermodynamic cis isomer, cis ‐PtCl2 (1 H2 ) (2 ), or the kinetic trans isomer, trans ‐PtCl2 (1 H2 ) (3 ). Both species have been fully characterized both in the solid state and in solution. Thermodynamic parameters for isomerization processes of2 and3 have been determined. Halide abstraction from2 and3 led to formation of cis ‐[Pt(CH3 CN)(Cl)(1 H2 )]BF4 and trans ‐[Pt(CH3 CN)(Cl)(1 H2 )]BF4 . Abstract : The design, synthesis and stereoselective coordination chemistry of a new ditopic diphosphine ligand toward Pt II are described. The cis and trans isomer of the PtCl2 complex are structurally characterized. Spectroscopic investigations on the conversion of the trans into the cis ‐isomer and formation of cationic derivatives are also presented.