Formation of Metallamacrocycles from Palladium(II), Platinum(II) and Copper(I) Complexes and the Ditopic Ligands [{ p ‐(Ph 2 PO)C 6 H 4 } 2 CMe 2 ], [{2‐Ph 2 PO‐3,5‐(Me 3 C) 2 C 6 H 2 } 2 S], [{ p ‐[(C 10 H 6 O) 2 PO]C 6 H 4 } 2 CMe 2 ]

The new ligands bis(phosphinito) [{2‐Ph 2 PO‐3,5‐(Me 3 C) 2 C 6 H 2 } 2 S] ( 4 ) and chiral bis(phosphite) [{ p ‐[(C 10 H 6 O) 2 PO]C 6 H 4 } 2 CMe 2 ] ( 5 ) were synthesised and their reactions with palladium(II), platinum(II), copper(I) substrates were studied. The ligand 3 [{ p ‐(Ph 2 PO)C 6 H 4 } 2 CMe 2 ], 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) 2 Cl 2 ] the metallamacrocycle [PdCl 2 (μ‐ 3 )] 2 ( 6 ) or the oligomer [Pd 2 Cl 4 (μ‐ 3 )] n ( 7 ) were formed, depending on the molar ratio used. The reaction of 3 with [Pd(η 3 ‐C 3 H 5 )Cl] 2 afforded compound {[Pd(η 3 ‐C 3 H 5 )Cl] 2 (μ‐ 3 )} ( 8 ). The allylpalladium macrocycle [Pd(η 3 ‐C 3 H 5 )(μ‐ 3 )] 2 [OTf] 2 ( 9 ) was obtained by treating a solution of 8 in THF with AgCF 3 SO 3 . The reactions of ligand 3 with [Pt(COD)I 2 ] or [Cu(NCCH 3 ) 4 ]BF 4 led to the formation of metallamacrocycles [PtI 2 (μ‐ 3 )] 2 ( 10 ) and [Cu 2 (μ‐ 3 ) 2 ][BF 4 ] 2 ·2CH 3 CN ( 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 {PdCl 2 {[2‐Ph 2 PO‐3,5(Me 3 C) 2 C 6 H 2 ][3,5‐(Me 3 C) 2 C 6 H 2 OH]S}] ( 12 ). The reaction between [Cu(NCCH 3 ) 4 ]BF 4 and 4 afforded the ionic metallamacrocycle [Cu(μ‐ 4 )][BF 4 ] 2 ·2CH 3 CN ( 14 ). In compound 10 , the size of the central cavity formed by the bridging ligand 3 was determined.