Influence of a thioether function in short-bite diphosphine ligands on the nature of their silver complexes: structure of a trinuclear complex and of a coordination polymer

New cationic Ag(I) complexes were prepared by reaction of AgBF4with two thioether-functionalizedbis(diphenylphosphino)amineligands, Ph2PN(p-ArSMe)PPh2(L1) and Ph2PN(n-PrSMe)PPh2(L2), and compared with those obtained from the unfunctionalizedligandsPh2PN(Ph)PPh2(L3) and Ph2PN(n-Bu)PPh2(L4), respectively. The complex [Ag3(μ3-Cl)2(μ2-L1-P,P)3](BF4) (1·BF4) contains a triangular array of Ag centres supported by three bridgingL1ligandsand two triply-bridging chlorides. In contrast,ligandL2led to the coordinationpolymer[{Ag2(μ3-L2,-P,P,S)2(MeCN)2}{Ag2(μ2-L2-P,P)2(MeCN)2}(BF4)4]n(2) in which the tethered thioether group connects intermolecularly a Ag2unit to the diphosphine bridging the other Ag2unit. WithL3andL4, two similar complexes were obtained, [Ag2(μ2-L3)(BF4)2] (3) and [Ag2(μ2-L4)(BF4)2] (4), respectively, with bridging diphosphineligandsand a BF4anion completing the coordination sphere of the metal. Complexes1·BF4·CH2Cl2,2·THF,3·3CH2Cl2and4have been fully characterized, including bysingle crystal X-ray diffraction.