Copper complexes of 1,3-bis(2-pyridyl)-1-thiapropane (bpt) andpyridine-2(1H)-thione. Crystal structure of[{Cu(µ-O2CMe)2(bpt)}2] and metal-promoted cleavage of bpt

The reactivity of the asymmetric thioether 1,3-bis(2-pyridyl)-1-thiapropane [1-(2-pyridyl)-2-(2-pyridylsulfanyl)ethane] (bpt) with copper-(I) and -(II) starting materials has been investigated. Reaction with [Cu(NCMe) 4 ]PF 6 in MeCN gave a cluster formulated as [Cu 4 (bpt) 6 ][PF 6 ] 4 , whilst reaction in tetrahydrofuran resulted in partial cleavage of bpt to give the mixed thionato–thioether complex [Cu 2 (SC 5 H 4 N)(bpt)]PF 6 [SC 5 H 4 NH = pyridine-2(1H)- thione]. Reaction with [Cu 2 (µ-O 2 CMe) 4 ] in MeOH gave the dimer [{Cu(µ-O 2 CMe) 2 (bpt)} 2 ], whose crystal structure shows that the bpt ligands are monodentate and co-ordinated via the N atom remote from the thioether. The compound bpt undergoes cleavage with other copper(II) salts such as Cu(BF 4 ) 2 , ultimately giving the hexameric copper(I) complex [Cu 6 (SC 5 H 4 N) 6 ]. The details of this reaction have been investigated. Reaction of SC 5 H 4 NH with Cu(NO 3 ) 2 in the presence of HNO 3 gave [Cu(NO 3 )(SC 5 H 4 NH) 2 ], which in turn reacted progressively with PPh 3 to give [Cu(NO 3 )(SC 5 H 4 NH) 2 (PPh 3 )] and the known complex [Cu(SC 5 H 4 NH) 2 (PPh 3 ) 2 ]NO 3 , whose crystal structure has been determined. Other complexes of SC 5 H 4 NH with copper(I) and a range of anions have been prepared, and the crystal structure of the dimer [Cu 2 (SC 5 H 4 NH) 6 ][MeC 6 H 4 SO 3 ] 2 is reported.