Formation of Metallamacrocycles from Palladium(II), Platinum(II) and Copper(I) Complexes and the Ditopic Ligands [{p‐(Ph2PO)C6H4}2CMe2], [{2‐Ph2PO‐3,5‐(Me3C)2C6H2}2S], [{p‐[(C10H6O)2PO]C6H4}2CMe2]

The new ligands bis(phosphinito) [{2-Ph2PO-3,5-(Me3C)2C6H2}2S] (4) and chiral bis(phosphite) [{p-[(C10H6O)2PO]C6H4}2CMe2] (5) were synthesised and their reactions with palladium(II), platinum(II), copper(I) substrates were studied. The ligand 3 [{p-(Ph2PO)C6H4}2CMe2], previously reported by us, was also used in the same reactions. Ligands 3 and 5 formed 28-membered metallamacrocycles while ligand 4 afforded the analogous compound only in the reaction with the copper(I) substrate. In the reaction of 3 with [Pd(PhCN)2Cl2] the metallamacrocycle [PdCl2(μ-3)]2 (6) or the oligomer [Pd2Cl4(μ-3)]n (7) were formed, depending on the molar ratio used. The reaction of 3 with [Pd(η3-C3H5)Cl]2 afforded compound {[Pd(η3-C3H5)Cl]2(μ-3)} (8). The allylpalladium macrocycle [Pd(η3-C3H5)(μ-3)]2[OTf]2 (9) was obtained by treating a solution of 8 in THF with AgCF3SO3. The reactions of ligand 3 with [Pt(COD)I2] or [Cu(NCCH3)4]BF4 led to the formation of metallamacrocycles [PtI2(μ-3)]2 (10) and [Cu2(μ-3)2][BF4]2·2CH3CN (11), respectively. The structure of 10 was also elucidated by X-ray analysis. Reactions of 4 with palladium(II) and platinum(II) complexes afforded a mixture of two very different compounds in almost an equimolar ratio. An X-ray analysis established that one is a mononuclear compound, formed by modification of the ligand 4, containing a P,S-chelate, namely {PdCl2{[2-Ph2PO-3,5(Me3C)2C6H2][3,5-(Me3C)2C6H2OH]S}] (12). The reaction between [Cu(NCCH3)4]BF4 and 4 afforded the ionic metallamacrocycle [Cu(μ-4)][BF4]2·2CH3CN (14). In compound 10, the size of the central cavity formed by the bridging ligand 3 was determined.