The molecular structures of (R(F))2Zn (3), (R(F))2Cd(MeCN) (4a), and (R(F))2Hg (5) have been determined by X-ray crystallography (R(F) = 2,4,6-tris(rifluoromethyl)phenyl). For 3: triclinic, P1BAR, a = 8.339 (3) angstrom, b = 9.064 (2) angstrom, c = 13.499 (4) angstrom, alpha = 88.38 (3)-degrees, beta = 87.79 (4)-degrees, gamma = 76.85 (2)-degrees, V = 992.6 (5) angstrom 3, Z = 2, and R = 3.92%. For 4a: monoclinic, P2(1)/c, a = 10.876 (3) angstrom, b = 16.79 (1) angstrom, c = 13.865 (5) angstrom, beta = 112.81 (2)-degrees, V = 2334 (2) angstrom 3, Z = 4, and R = 3.49%. For 5: monoclinic, P2(1)/n, a = 8.842 (2) angstrom, b = 7.891 (2) angstrom, c = 15.294 (3) angstrom, beta = 92.20 (3)-degrees, V = 1066.3 (4) angstrom 3, Z = 2, and R = 5.73%. A characteristic structural feature of all three derivatives is weak metal-fluorine interactions. (R(F))2Zn and (R(f)2Cd(MeCN) represent the first examples of structurally characterized two- and three-coordinate monomeric diarylzinc and -cadmium compounds, respectively.