The reactivity of (eta5-C5Me5)2Sm (1) with polycyclic aromatic hydrocarbons and related nitrogen heterocycles has been examined. 1 reacts in arenes with substrates which have reduction potentials more positive than -2.22 V vs SCE to form a series of unusual bimetallic complexes in high yield. 1 reacts with anthracene to form [(eta5-C5Me5)2-Sm]2[mu-eta3:eta3-(C14H10)] (2) in which a planar C14H10 unit is coordinated on each side by a (C5Me5)2Sm moiety with shortest Sm-C distances of 2.595(4), 2.840(4), and 2.791(4) angstrom for the C(9), C(9a), and C(1) carbon atoms (anthracene numbering), respectively. Pyrene reacts with 1 to form [(eta5-C5Me5)2SM]2[mu-eta:eta-(C16H10)] (3) in which the two (C5Me5)2Sm units also coordinate to opposite sides of the planar polycyclic system, but they are on the same end of the tetracyclic unit. 2,3-Benzanthracene reacts with 1 to form an analog of 2, [(eta5-C5Me5)2SM]2[mu-eta3:eta5(C18H12)] (4). 1 also reacts with 9-methylanthracene and acenaphthylene to form [(C5Me5)2SM]2(C15H12) (5) and [(C5Me5)2-Sm]2(C12H8) (6), respectively, in high yields. In contrast, the reaction of azulene with 1 generates (eta5-C5Me5)3Sm. Phenazine reacts with 1 to produce [(eta5-C5Me5)2Sm]2[mu-eta3:eta3-(C12H8N2)] (7), which is very similar to 2 except that it contains a 2.360(2) angstrom Sm-N bond. In contrast, acridine is reductively coupled by 1 to form [(eta5-C5Me5)2Sm]2-mu-eta3:eta3-(C13H9N)2] (8), which contains nonplanar C13H9N units. 2 crystallizes from toluene in the triclinic space group P1BAR [C1(1):No. 2] with unit cell parameters a = 10.495(2) angstrom, b = 11.2361(14) angstrom, c = 11.2857(12) angstrom, alpha = 80.953(9)degrees, beta = 85.463 (11)degrees, gamma = 76.657(12)degrees, V = 1277.6(3) angstrom3, and D(calcd) = 1.445 Mg m-3 for Z = 1. inement of the model based on 3298 reflections (F(o) > 0) converged to a final R(F) = 2.8%. 3 crystallizes from benzene in the monoclinic space group P2(1)n [C(2h)5; No. 14] with unit cell parameters a = 16.528(2) angstrom, b = 11.3716(16) angstrom, c = 25.433(2) angstrom, beta = 101.194(9)degrees, V = 4689.1(10) angstrom3, and D(calcd) = 1.479 Mg m-3 for Z = 4.