The reactions of unsymmetric phosphorus ylides of the type [Ph2P(CH2)nPPh2C(H)C(O)C6H4‐p‐CN] (n = 1 (Y1); n = 2 (Y2)) with C60 and M(dba)2 (M = Pd or Pt; dba = dibenzylideneacetone) are reported. Based on the various coordination modes of these ylides in complexation, the following new Pd/Pt–cyclopropa[60]fullerene complexes were obtained: P,C‐coordinated [(η2‐C60)Pd(κ2‐Y1)] (1) and [(η2‐C60)Pt(κ2‐Y1)] (2) complexes and P‐coordinated [(η2‐C60)Pd(Y2)2] (3) and [(η2‐C60)Pt(Y2)2] (4) complexes. These compounds were characterized using Fourier transform infrared, UV–visible and NMR (1H, 13C and 31P) spectroscopies and scanning electron microscopy. Furthermore, cytotoxicity studies showed that nanoparticles of these complexes can be used as non‐toxic labels for cellular imaging application. Also energy decomposition analysis results revealed that the percentage contribution of ΔEelec in total interaction energy is considerably larger than that of ΔEorb. Thus, in all complexes the (η2‐C60)M(Y1) bond is considerably more electrostatic in nature than the (η2‐C60)M(Y1) bond. Finally, by application of the Taguchi method for optimization of parameters in Suzuki–Miyaura reaction, the catalytic activity of Pd complexes 1 and 3 was investigated in the cross‐coupling reaction of various aryl chlorides with phenylboronic acid. According to analysis of variance results, solvent has the highest F value and it has high contribution percentage (36.75%) to the yield of Suzuki–Miyaura reaction.
New P,C-coordinated Pd/Pt-complexes were characterized successfully and the cytotoxic studies showed that they can be used as non-toxic labels for cellular imaging.
The reaction of α‐keto‐stabilized diphosphine ylides [Ph2P(CH2)nPPh2═C(H)C(O)C6H4‐p‐CN] (n = 1 (Y1); n = 2 (Y2)) with dibromo(1,5‐cyclooctadiene) palladium(II)/platinum(II) complexes, [Pd/PtBr2(cod)], in equimolar ratio gave the new cyclometalated Pd(II) and Pt(II) complexes [Br2Pd(κ2‐Y1)] (1), [Br2Pt(κ2‐Y1)] (2), [Br2Pd(κ2‐Y2)] (3) and [Br2Pt(κ2‐Y2)] (4). These compounds were screened in a search for novel antibacterial agents and characterized successfully using Fourier transfer infrared and NMR (1H, 13C and 31P) spectroscopic methods. Also, the structures of complexes 1 and 2 were characterized using X‐ray crystallography. The results showed that the P,C‐chelated complexes 1 and 2 have structures consisting of five‐membered rings, while 3 and 4 have six‐membered rings, formed by coordination of the ligand through the phosphine group and the ylidic carbon atom to the metal centre. Also, a theoretical study of the structures of complexes 1–4 was conducted at the BP86/def2‐SVP level of theory. The nature of metal–ligand bonds in the complexes was investigated using energy decomposition analyses (EDA) and extended transition state combined with natural orbitals for chemical valence analyses. The results of EDA confirmed that the main portions of ΔEint, about 57–58%, in the complexes are allocated to ΔEelstat.
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