Formation of metallamacrocycles from palladium(II), platinum(II) and copper(I) complexes and the ditopic ligands [{p-(Ph2PO)C6H4}(2)CMe2], [{2-Ph2PO-3,5-(Me3C)(2)C6H2}(2)S], [{p-[(C10H6O)(2)PO]C6H4}(2)CMe2]

The new ligands bis (phosphinito) [{2-Ph2PO-3,5-(Me3C)(2)C6H2)(2)S] (4) and chiral bis(phosphite) [{p-[C-10 [(C10H6O)(2)PO]C6H4](2)CMe2] (5) were synt hesised and their reactions with palladium(II), platinum(II), copper(I) sub strates were studied. The ligand 3 [{p-(Ph2PO)C6H4}(2)CMe2], previously rep orted by us, was also used in the same reactions. Ligands 3 and 5 formed 28 -membered metallamacro-cycles while ligand 4 afforded the analogous compoun d only in the reaction with the copper(I) substrate. In the reaction of 3 w ith [Pd(PhCN)(2)Cl-2] the metallamacrocycle [PdCl2(mu -3)](2) (6) or the ol igomer [Pd2Cl4(mu -3)](n) (7) were formed, depending on the molar ratio use d. The reaction of 3 with [Pd(eta (C3H5)-C-3)Cl](2) afforded compound {[Pd( eta (3)-C3H5)Cl](2)(mu -3)} (8). The allylpalladium macrocycle [Pd(eta (3)- C3H5) (mu -3)](2)[OTf](2) (9) was obtained by treating a solution of 8 in T HF with AgCF3SO3. The reactions of ligand 3 with [Pt(COD)I,I or [Cu(NCCH3)( 4)]BF4 led to the formation of metallamacrocycles [PtI2(mu -3)](2) (10) and [Cu-2(mu -3)(2)][BF4](2). 2CH(3)CN (11), respectively. The structure of 10 was also elucidated by X-ray analysis. Reactions of 4 with palladium(II) a nd piatinum(II) complexes afforded a mixture of two very different compound s 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{[2Ph(2)PO-3,5(Me3C)(2)C6H2][3,5-(Me3C)(2)C6H2OH ] (12). The reaction between [Cu(NCCH3)(4)]BF4 and 4 afforded the ionic met allamacrocycle [Cu(mu -4)][BF4](2). 2CH(3)CN (14). In compound 10, the size of the central cavity formed by the bridging ligand 3 was determined.