The synthesis of some binuclear ruthenium(I) complexes bridged by anionic groups. X-ray structures of pyrazolate- and oxypyridinate-bridged complexes

Article abstract of DOI:10.1016/0022-328X(89)87007-X

A series of binuclear ruthenium(I) complexes, , have been prepared by two closely related routes.Complexes 2 (XY^- = S2NC3H4^-) and 3 (XY^- = NC5H4O^-) have been prepared by the reaction of with sodium 2-mercaptothiazolinate and sodium 2-oxypyridinate, respectively.The related pyrazolate-bridged complex 4 (XY^- = N2C3H3^-) was prepared by the reaction of sodium pyrazolate with followed by addition of PPh3.The X-ray structures of compounds 3 and 4 have been determined.Compound 3 crystallizes in the triclinic space group P1<*> with a 14.766(2), b 15.821(2), c 10.745(3) Angstroem, α 98.28(2) deg, β 11.99(2) deg, γ 103.29(1) deg, V 2209.1 Angstroem³, Z = 2.On the basis of 5521 unique observations (NO) and 379 parameters varied (NV) the structure has been refined to R = 0.042 and R_w = 0.054.Compound 4 crystallizes in the orthorombic space group P2₁2₁2₁ with a 13.220(2), b 14.864(4), c 21.403(3) Angstroem, V 4200.7 Angstroem³ and Z = 4.This structure has been refined to R = 0.041 and R_w = 0.023 for NO = 3915 and NV = 546.Both structures display the sawhorse arrangement of carbonyl groups and have the phosphine ligands in the axial positions opposite the Ru-Ru binds.For 3 the oxypyridinate groups are bound in a head-to-tail arrangement.The two-atom pyrazolate bridge imparts more strain than the three-atom oxypyridinate bridge and as a result the equatorial planes of the Ru centers are tipped by only 16.2(4) deg in 3 but by 35.4(1) deg in 4.The Ru-Ru distances (2.7108(4) Angstroem (3); 2.732(1) Angstroem (4)) correspond to normal single bonds.