Reactions of Re-2(CO)(8)(mu-C6H5)(mu-H), 1, with naphthalene and anthracene have yielded the first multiply-CH activated arene products through the reductive elimination of benzene from 1 and multiple oxidative-additions of the dirhenium octacarbonyl grouping to these polycyclic aromatic compounds under very mild conditions. In addition, compound 1 was found to react with itself to yield the bis-Re-2-metalated C6H4 bridged compound Re-2(CO)(8)(mu-H)(mu-1,mu-3-C6H4)Re-2(CO)(8)(mu-H), 3. Reaction of 1 with naphthalene yielded two doubly CH activated isomers, Re-2(CO)(8)(mu-H)(mu-eta(2)-1,2-mu-eta(2)-3,4-C10H6)Re-2(CO)(8)(mu-H), 4, 41% yield, and Re-2(CO)(8)(mu-H)(mu-eta(2)-1,2-mu-eta(2)-5,6-C10H6)-Re-2(CO)(8)(mu-H), 5, via the mono CH activated intermediate Re-2(CO)(8)(mu-eta(2)-C10H7)(mu-H), 2. Compound 4 contains two Re-2(CO)(8)(mu-H) groups on one C-6 ring formed by CH activations at the 2- and 4-positions. Compound 5 contains two Re-2(CO)(8)(mu-H) groups; one formed by CH activation at the 2-position on one C-6 ring and the other formed by CH activation at the 6-position (or centrosymmetrically related 2'-position) on the second C-6 ring. The Re-2(CO)(8)(mu-H) groups are coordinated to the C-6 rings by binuclear sigma + pi coordination to two adjacent carbon atoms in the rings. Compound 1 reacts with anthracene to yield the mono-CH activated compound Re-2( CO)(8)(mu-eta(2)-1,2-C14H9) (mu-H), 6, and two doubly CH activated compounds, Re-2(CO)(8)(mu-H)(mu-eta(2)-1,2-mu-eta(2)-3,4-C14H8)Re-2(CO)(8)(mu-H), 7, and Re-2(CO)(8)(mu-H)(mu-eta(2)-1,2-mu-eta(2)-5,6-C14H8)Re-2(CO)(8)(mu-H), 8. Compounds 7 and 8 are isomers that are structurally similar to 4 and 5. Compounds 7 and 8 can also be obtained in good yields from the reaction of 6 with 1. In the presence of a 5/1 ratio of 1/anthracene, a small amount (5% yield) of the tetra-substituted anthracene product [Re-2( CO)(8)(mu-H)](4)(mu-eta(2)-1,2-mu-eta(2)-3,4-mu-eta(2)-5,6-mu-eta(2)-7,8-C14H6), 9, was formed. Compound 9 contains four sigma + pi coordinated Re-2(CO)(8)(mu-H) groups formed by oxidative additions of the CH bonds of anthracene to the Re-2(CO)(8) groups at the 2, 4, 6, and 8 positions of the three ring system. Molecular orbital calculations have been performed for all new compounds in order to develop an understanding of the bonding of the ring systems to the Re-2(CO)(8)(mu-H) groups. All new compounds were characterized by single-crystal X-ray diffraction analyses.