The trinucleating ligand 2,3,8,9,14,15-hexamethyl-5,6,11,12,17,18 (hhtn), 1, has been obtained in an efficient one-pot synthesis. The reaction of a yellow-green solution of 1 with 1 equiv of Pd(NCPh)(2)Cl-2 gives orange PdCl2(hhtn), 2, which crystallizes with two independent PdCl2(hhtn) molecules, a molecule of chlorobenzene, and two molecules of methanol in the triclinic space group P (1) over bar with a 12.949(3) A, b = 16.625(4) Angstrom, c 17.062(4) Angstrom, a 63.00(2)degrees, beta = 71.39(2)degrees, and gamma = 79.78(2)degrees at 130 K with Z = 4. Refinement of 5551 reflections and 387 parameters yielded R = 0.059 and R(w) = 0.060. The structure consists of a nearly square planar PdCl2(N-2) complex in a highly-distorted hhtn framework. Unfavorable Cl... H interactions force the PdCl2 unit out of the hhtn plane by 28.1 degrees. The structure indicates that there are pi-pi (ligand-ligand) interactions. Reaction of 2 with another equivalent of Pd(NCPh)(2)Cl-2 produces the binuclear species (PdCl2)(2)(hhtn), 5. Addition of Re(CO)(5)Cl to 1 in refluxing toluene affords deep red crystals of fac-Re(CO)(3)Cl(hhtn), 3. Dark red needles of Re(CO)(3)Cl(hhtn) CH3OH form in the monoclinic space group P2/n with a 10.515(2) Angstrom, b = 27.123(6) Angstrom, c 11.385(2) Angstrom, and beta = 110.95(2)degrees at 130 K with Z = 4. Refinement of 5451 reflections and 415 parameters yielded R = 0.052 and R(w) = 0.052. The structure features a nearly octahedral Re center that is deflected from the hhtn plane by 19.5 degrees. The hhtn in 3 is less distorted than in 2. Reaction of a dichloromethane solution of 3 with 1 equiv of Pd(NCPh)(2)Cl-2 produces the heterobinuclear (Re(CO)(3)Cl)(PdCl2)(hhtn), 4. Red-brown blocks of 4 cocrystallize with 2.6 molecules of 1,2-dichlorobenzene in the triclinic space group P (1) over bar with a 14.540(4) Angstrom, b = 14.558(3) Angstrom, c 14.671(4) Angstrom, alpha 64.72(2)degrees, 18 = 66.00(2)degrees, and gamma = 63.30(2)degrees at 130 K with Z = 2. Refinement based on full-matrix least squares on F-2 using 8481 reflections and 513 parameters yielded R = 0.061 and R(2) = 0.135. The structure includes a nearly octahedral Re and a square planar Pd coordinated to a highly distorted hhtn ligand. The PdCl2 fragment is bent out of the ligand plane by 40.2 degrees, whereas the Re unit is distorted by only 10.4 degrees. Complex 4 forms pi-pi stacks exclusively with the 1,2-dichlorobenzene solvate molecules.