Palladium(II) and Platinum(II) Complexes with Heteroditopic 10-(Aryl)phenoxarsine (Aryl = 2-C<sub>6</sub>H<sub>4</sub>OR, R = H, Me, Pr<sup><i>i</i></sup>) Ligands: Solvent-Oriented Crystallization of cis Isomers
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The synthesis and characterization of 10-(o-alkoxyphenyl)phenoxarsines 2-ROC6H4As(C6H4)2O (R = H, Me, and Pri, As(C6H4)2O = phenoxarsine) and their platinum(II) and palladium(II) complexes cis-[PtCl2{2-PriOC6H4As(C6H4)2O-κAs}2] (1), trans-[PdCl2{2-PriOC6H4As(C6H4)2O-κAs}2] (2), cis-[PtCl2{2-HOC6H4As(C6H4)2O-κAs}2] (3), cis-[PdCl2{2-HOC6H4As(C6H4)2O-κAs}2] (4), cis-[PtI2{2-MeOC6H4As(C6H4)2O-κAs}2] (5), and trans-[PdCl2{2-MeOC6H4As(C6H4)2O-κAs}2] (6) are reported. The chelate complex cis-[Pt{2-OC6H4As(C6H4)2O-κAs,O}2] (7) is also described. The molecular structures of 1–4 and 7 were determined. The short As···O intramolecular interaction found in complexes 1–4 in the solid state was also verified by calculations at the B3LYP/LANL2DZ level for complex 2 and for 10-(o-isopropoxyphenyl)phenoxarsine in the gas phase, and this suggests that the interaction is a characteristic of the ligand rather than a packing effect. Calculations at the B3LYP/LANL2DZ and Oniom(B3LYP/LANL2DZ:uff) levels for complexes 1–4 showed that the solvent plays a crucial role in the crystallization (through geometry constraints) of the kinetically stable cis isomers.
