Cu(I) and Ag(I) complexes of two sterically demanding Xylyl-Substituted phosphine Ligands: Synthesis, Characterization, and structural examination

•PR2Xyl phosphines (R = iPr, tBu) react with CuX (X = Cl, Br, I) to form a series of dinuclear complexes of the general formula [Cu(μ-X)PR2Xyl]2.•The shortest Cu∙∙∙Cu separations of ca. 2.8 Å found in the iodide derivatives [Cu(μ-I)PR2Xyl]2 are consistent with d10-d10 bonding interactions.•Homo-bimetallic complexes [M(μ-OTf)PR2Xyl]2 (M = Cu, Ag) incorporate 8-membered cyclic cores with Ci or Ci-like symmetry and twist-chair conformation.•[Cu(PiPr2Xyl)2]+ cations are 2-coordinate complexes with PCuP angles of ca. 168-169°, staggered conformations, and synclinal disposition of the Xyl groups with respect to the P∙∙∙P axis.