An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The synthesis of palladacyclic derivatives with the hybrid pyridylphosphine ligands Py(CH2)OPPh2 (a) and PyNHPPh2 (b) in a neutral P,N-chelating coordination mode has been achieved. Treatment of selected chloride-bridged cyclometallated precursors [Pd(C∧N)(μ-Cl)]2 [C∧N=2-pyridinin-phenyl Phpy, I-compounds; 7,8-benzoquinolyl Bzq, II-compounds; phenylazophenyl Azb, III-compounds or 2-(2-oxazolinyl)phenyl Phox, IV-compounds] with a or b in the presence of stoichiometric KPF6 gave the mononuclear derivatives Ia–IVa and Ib–IVb. The crystal structures of compounds [Pd(Azb)(Ph2POCH2Py-P,N)][PF6] (IIIa) and [Pd(Phpy)(Ph2PNHPy-P,N)][PF6] (Ib) have been determined. The new palladacyclopentadiene precursor [Pd{C4COOMe4}(CH3CN)2] (V) has been prepared starting from the polymeric complex [Pd{C4COOMe4}]n. Its usefulness in the preparation of new derivatives has been tested by means of the straightforward reaction with ligands (a) or (b) to give mononuclear compounds [Pd{C4(COOMe)4}(Ph2POCH2Py-P,N)] (Va) and [Pd{C4(COOMe)4}(Ph2PNHPy-P,N)] (Vb). The reactions of hydroxo-bridged precursors [Pd(C∧N)(μ-OH)]2 or [Pd2{C4(COOMe)4}2 (μ-OH)2][NBu4]2 with PyNHPPh2 afforded mononuclear complexes Ic–Vc (PyNPPh2-=cligand) in which a less common anionic P,N-binding mode is forced as a result of ligand deprotonation. The new complexes were characterised by partial elemental analyses and spectroscopic methods (IR, FAB, 1H and 31P{1H} NMR).

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The coordination properties of hybrid phosphino-amide ligands omicron-Ph2PC6H4CONHR [R = Pr-i (a), Ph (b)] have been investigated. New cyclometallated palladium(II) complexes in which a and b act as P-monodentate ligands have been synthesised by reacting them with selected cyclometallated precursors containing bridging chloride or acetate groups. The crystal structures of the compounds [Pd(Bzq)(o-Ph2PC6H4CO-(NHPr)-Pr-i)(Cl)] and [Pd(Phox)(o-Ph2PC6H4CO-(NHPr)-Pr-i)(CH3COO)] (Bzq = 7,8-benzoquinolyl; Phox = 2-(2-oxazolinyl)phenyl) have been determined. Hemilability of coordinated ligand b is detected when it appears combined with certain cyclometallated backbones. A rigid P,O-chelating behaviour of the ligands, confirmed by the crystal structure determination of [Pd(Bzq)(omicron-Ph2PC6H4CO-(NHPr)-Pr-i)][PF6], is observed in complexes obtained by adding stoichiometric KPF6 to [Pd(C<^>N)(mu-Cl)](2) compounds. The reactions of hydroxo-bridged precursors [Pd(C<^>N)(p-OH)](2) with a and b afforded mononuclear derivatives in which a less common anionic P,N-binding mode is exhibited. The crystal structure of Pd(Phpy)(omicron-Ph2PC6H4CO-(NPr)-Pr-i)] (Phpy = 2-phenylpyridine) is also reported. Furthermore, related compounds with phosphino-carboxylate ligands have been prepared by direct reaction between 2-(diphenylphosphinobenzoic) acid and [Pd(C<^>N)-(mu-CH3COO)](2) precursors, and the X-ray structures of [Pd(C<^>N)(omicron-Ph2PC6H4COO)] (C<^>N = Bzq and Phpy) have been determined.