Coinage Metal Complexes of Bis(quinoline‐2‐ylmethyl)phenylphosphine‐Simple Reactions Can Lead to Unprecedented Results.

The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline‐2‐ylmethyl)phenylphosphine (bqmpp) towards selected CuI, AgI and AuI species is described. The resulting X‐ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)4]BF4, compound 1 [Cu2(bqmpp)2](BF4)2 is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π‐stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). CuI complex 2 [Cu4Cl3(bqmpp)2]BF4 contains a rarely observed Cu4Cl3 cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF6] with the ligand leads to a dinuclear compound (3) in solution as confirmed by 31P{1H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3, a tris(quinoline‐2‐ylmethyl)bisphenyl‐phosphine (tqmbp) compound [Ag2(tqmbp)2](SbF6)24 is formed by elimination of quinaldine. The Au(I) compound [Au2(bqmpp)2]PF6 (5) is prepared as expected and shows a linear arrangement of two phosphine ligands around AuI. [ABSTRACT FROM AUTHOR]