The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine ( bqmpp ) towards selected Cu
I, Ag
I and Au
I species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)
4]BF
4, compound 1 [Cu
2(bqmpp)
2](BF
4)
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). Cu
I complex 2 [Cu
4Cl
3(bqmpp)
2]BF
4 contains a rarely observed Cu
4Cl
3 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[SbF
6] 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 [Ag
2(tqmbp)
2](SbF
6)
2 4 is formed by elimination of quinaldine. The Au(I) compound [Au
2(bqmpp)
2]PF
6 ( 5 ) is prepared as expected and shows a linear arrangement of two phosphine ligands around Au
I.
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