Formula: C46H46O4P2Pd2. So far, in addition to halogen atoms, other non-metallic atoms can become part of the aromatic heterocycle, and the target ring system is still aromatic. Compound: trans-Di-μ-acetatobis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium, is researched, Molecular C46H46O4P2Pd2, CAS is 172418-32-5, about Cyclometalated Pt(II) and Pd(II) complexes with a trithiacrown ligand.
The synthesis and full characterization for a series of cyclometalated complexes of Pt(II) and Pd(II) incorporating the fluxional trithiacrown ligand 1,4,7-trithiacyclononane ([9]aneS3) is reported. Reaction of [M(C-N)(μ-Cl)]2 (M = Pt(II), Pd(II); C-N = 2-phenylpyridinate (ppy) or 7,8-benzoquinolinate (bzq)) with [9]aneS3 followed by metathesis with NH4PF6 yields [M(C-N)([9]aneS3)](PF6). The complexes [M(C-P)([9]aneS3)](PF6) (M = Pt(II), Pd(II); C-P = {CH2C6H4P(o-tolyl)2-C,P}-) were synthesized from their resp. [Pt(C-P)(μ-Cl)]2 or [Pd(C-P)(μ-O2CCH3)]2 (C-P) starting materials. All five new complexes have been fully characterized by multinuclear NMR, IR and UV-Vis spectroscopies in addition to elemental anal., cyclic voltammetry, and single-crystal structural determinations As expected, the coordinated [9]aneS3 ligand shows fluxional behavior in its NMR spectra, resulting in a single 13C NMR resonance despite the asym. coordination environment of the cyclometalating ligand. Electrochem. studies reveal irreversible one-electron metal-centered oxidations for all Pt(II) complexes, but unusual two-electron reversible oxidations for the Pd(II) complexes of ppy and bzq. The x-ray crystal structures of each complex indicate an axial M-S interaction formed by the endodentate conformation of the [9]aneS3 ligand. The structure of [Pd(bzq)([9]aneS3)](PF6) exhibits disorder in the [9]aneS3 conformation indicating a rare exodentate conformation as the major contributor in the solid-state structure. DFT calculations on [Pt([9]aneS3)(ppy)](PF6) and [Pd([9]aneS3)(ppy)](PF6) indicate the HOMO for both complexes is primarily dz2 in character with a significant contribution from the Ph ring of the ppy ligand and p orbital of the axial sulfur donor. In contrast, the calculated LUMO is primarily ppy π* in character for [Pt([9]aneS3)(ppy)](PF6), but dx2-y2 in character for [Pd([9]aneS3)(ppy)](PF6).
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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate