FACILE SYNTHESES, ISOMERIC STRUCTURES, AND CHEMICAL-REACTIVITY OF DIRUTHENIUM(I) COMPLEXES RU-2(CO)(4)(MECN)(4)L(2)]X(2) (L=MECN, PPH(3),PPH(2)(ALLYL), PME(3), X(-)=PF6-, BF4-) - A CONVENIENT ROUTE TO 1,2-DIAMIDES AND 1,2-DITHIOLATES

Alkylating agents such as Et(3)O(+)X(-) (X(-) = PF6- or BF4-) readily remove the bridging acetate groups of [Ru-2(CO)(4)(O(2)CMe)(2)L(2)] at ambient temperature to give the versatile complexes [Ru-2(CO)(4)(NCMe )(4)L(2)]X(2) (L = MeCN (1), PPh(3) (2), PPh(2)(allyl) (3), and PMe(3) (4)). The crystal structures of 3 and 4 were determined by X-ray cryst allography: [3][BF4](2), a = 20.292(6), b = 17.223(7), c = 15.186(3), beta = 113.324(18)degrees, V = 4873(3) Angstrom(3), monoclinic C2/c, Z = 4, refined to R = 0.045, R(w) = 0.048, and GOF = 2.27. [4][BF4](2), a 12.570(4), b = 14.251(5), c 18.773(6) Angstrom, beta = 104.96(3)deg rees, V = 3251(9) Angstrom(3), monoclinic P2(1)/n, Z = 4, refined to R = 0.044, R(w) = 0.044, and GOF = 1.53. Although 3 adopts a trans-stag gered structure, 4 is in a cis-staggered geometry. The high reactivity of 1-4 is demonstrated via the cation-anion annihilation between 2(2) and the doubly deprotonated anion, (E-E)(2-), to give [Ru-2(CO)(4)-{ mu-eta(2),eta(2)-(E-E)}(PPh(3))(2)] ((E-E)(2-) = 1,2-(NH)(2)C6H42- (7) ; 2,3-(NH)(2)(CH62-)-H-10 (8); 1,2-(NH)(2)-4,5-Cl2C6H22- (9); 1,2-(NH) (2)-4,5-Me(2)C(6)H (2) (10); 9,10-(NH)(2)C14H8 (11); and 1,2-S2C6H42- (12)). The structures of 7-12 were also confirmed by an X-ray single-c rystal structure of 12: a 11.155(1), b = 21.302(2), c = 10.183(2) Angs trom, alpha = 93.65(1), beta = 113.43(1), gamma = 101.19(1)degrees, V = 2151.2(6) Angstrom(3), triclinic P ($) over bar 1, Z = 2, refined to R = 0.038, R(w) = 0.046, and GOF = 2.81. The Ru-Ru distances are 2.86 47(11) Angstrom in 3, 2.861(1) Angstrom in 4, and 2.6767(5) Angstrom i n 12.