Synthesis of Pt(II) phosphinocarboxylate complexes with auxiliary arylcarbene ligands and factors that control their stereochemistry

Orthoplatinated complexes [Pt(C boolean AND C*)(acac)] (1(R)), in which C boolean AND C* is orthoplatinated 3-R-1-phenyl-1H-benzo[d]imidazol-2-ylidene and R = Me and Ph, reacted with 10-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) under protonation of the acetylacetonate ligand (acac) to produce the corresponding phosphinocarboxylate bischelate complexes [Pt(C boolean AND C*)(dpf-kappa O-2,P)] (2(R)) as single isomers with trans-P,C(carbene) geometry. The compounds were fully characterized by elemental analysis, spectroscopic methods, single-crystal X-ray diffraction analysis, and cyclic voltammetry. In addition, DFT calculations were used to determine differences in energy and the bonding situation between 2(R) and the hypothetical geometric isomers 3(R) with a trans-P,C(phenyl) arrangement. The experimental and theoretical results are consistent with the antisymbiosis effect observed in complexes of soft metal ions, namely with weakening of Pt-C bonds by strongly trans-influencing ligands.

Automated summary

This study investigates the reaction between Orthoplatinated complexes [Pt(C boolean AND C*)(acac)] and Hdpf, resulting in the formation of new phosphinocarboxylate bischelate complexes [Pt(C boolean AND C*)(dpf-kappa O-2,P)]. Experimental and theoretical analysis reveals that the anti-symbiosis effect weakens the Pt-C bonds in these complexes.