title: PalladiumII and platinumII complexes with heteroditopic 10-(aryl)phenoxarsine (aryl = 2-C6H4OR, R = H, Me, Pr(i)) ligands: solvent-oriented crystallization of cis isomers.
abstract: 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-kappaAs}2] (1), trans-[PdCl2{2-PriOC6H4As(C6H4)2O-kappaAs}2] (2), cis-[PtCl2{2-HOC6H4As(C6H4)2O-kappaAs}2] (3), cis-[PdCl2{2-HOC6H4As(C6H4)2O-kappaAs}2] (4), cis-[PtI2{2-MeOC6H4As(C6H4)2O-kappaAs}2] (5), and trans-[PdCl2{2-MeOC6H4As(C6H4)2O-kappaAs}2] (6) are reported. The chelate complex cis-[Pt{2-OC6H4As(C6H4)2O-kappaAs,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.
authors.affiliation: Department of Chemistry, Babes-Bolyai University, Kogalniceanu 1, RO-400084, Cluj-Napoca, Romania.
authors.forename: Natalia
authors.initials: N
authors.lastname: Moldovan
authors.forename: Peter
authors.initials: P
authors.lastname: Lönnecke
authors.forename: Ioan
authors.initials: I
authors.lastname: Silaghi-Dumitrescu
authors.forename: Luminita
authors.initials: L
authors.lastname: Silaghi-Dumitrescu
authors.forename: Evamarie
authors.initials: E
authors.lastname: Hey-Hawkins
mesh_terms: D001152:Arsenicals / Q000737:chemistry*; D003460:Crystallization; D018360:Crystallography, X-Ray; D007536:Isomerism; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D010165:Palladium / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
chemical_list: D001152:Arsenicals; D008024:Ligands; D012997:Solvents; D010984:Platinum; D010165:Palladium; C006633:arsine