The ligand L = Ph2PCH2CHEtOPPh2 (R,S) with two chemically different donor sites and a center of chirality in the middle of the loop connecting the phosphorus atoms has been chosen for the preparation of a series of gold(I), silver(I), and copper(I) complexes. The ligand-to-metal ratio was allowed to vary between 2:1, 1:1, and 1:2. The 1:1 complexes [LAuX](2) with X = Cl, Br, I, and SCN have been found to be components of solution equilibria (in di- or trichloromethane) of various cyclic dinuclear isomers involving also several complexes generated in ligand redistribution processes. However, single crystals (X = Cl, Br) obtained from these solutions are composed solely of centrosymmetrical dimers where the two metal atoms are part of 12-membered rings and are bridged transannularly by two halogen atoms. By symmetry, the metal bridging by the two ligands L follows a head-to-tail pattern and involves a pair of enantiomers of L. The silver compound [LAgClO4](2) has an analogous structure with the silver atoms attaining coordination number 4 by perchlorate bridging. The copper complex [LCuCl](2) is a tricyclic binuclear compound where each copper atom is chelated by an individual ligand L and doubly halogen bridged with the second metal atom. The 2:1 complex [L2Au]Cl is assigned a bis-chelated structure with the tetracoordinated metal atom as a spiro center of two six-membered rings. The solution P-31 NMR spectra show the presence of various stereoisomers which are readily identified via the strong couplings mediated by the metal center. Only small J(P, P') values would be expected for P-P' coupling along the ligand PCCOP' loops. The spectrum of the dinuclear 1:2 complex L(AuCl)(2) features only two singlet P-31 resonances.