SYNTHESIS AND REACTION CHEMISTRY OF NEW ETA-5-CYCLOPENTADIENYLRUTHENIUM(II) AMINE AND AMIDE COMPLEXES

The complex eta-5-cpRuCl(Cy2PCH2PCy2) has been prepared from the reaction of ruthenium trichloride, cyclopentadiene, and Cy2PCH2CH2PCy2. Treating eta-5-cpRuCl(Cy2PCH2CH2PCy2) with silver triflate in THF solvent gives [eta-5-cpRu(Cy2PCH2PCy2]CF3SO3. Treating eta-5-cpRuClLL' with silver trilfate in THF solvent followed by ammonia gives the ammine complexes [eta-5-cpRu(NH3)LL']CF3SO3 (L = L' = PPh3; L = PPh3, L' = P(OMe)3; LL' = Cy2PCH2CH2PCy2). The analogous procedure using amines in place of ammonia gives the amine complexes [eta-5-cpRu(NH2R)LL']CF3SO3 (R = Me: L = L' = PPh3; L = PPh3, L' = P(OMe)3; LL' = Cy2PCH2CH2PCy2. R = CMe3: L = PPh3, L' = P(OMe)3. R = 1-C8H17: LL' = Cy2PCH2CH2PCy2). Metathetical replacement of the chloride ion in eta-5-cpRuCl(Cy2PCH2PCy2) by hydride or isocyanate ion gives eta-5-cpRuX(Cy2PCH2CH2PCy2) (X = H, NCO). Treating [eta-5-cpRu(NH3)(Cy2PCH2CH2PCy2)]+ with potassium hydride gives the amide complex eta-5-cpRu(NH2)(Cy2PCH2CH2PCy2). This amide complex reacts with Me4N+ to give [eta-5-cpRu(NH2Me)(Cy2PCH2CH2PCy2)]+. Passing CO through a solution of eta-5-cpRu(NH2)(Cy2PCH2CH2PCy2) gives the carbamoyl complex eta-5-cpRu(C(O)NH2)(Cy2PCH2CH2PCy2). Passing CO2 through a solution of eta-5-cpRu(NH2)(Cy2PCH2CH2PCy2) gives the carbamate complex eta-5-cpRu(OCONH2)(Cy2PCH2CH2PCy2). In anhydrous solution this carbamate complex loses water to give the isocyanate complex eta-5-cpRu(NCO)(Cy2PCH2CH2PCy2). Treating [eta-5-cpRu(NH2Me)(Cy2PCH2CH2PCy2)]+ with potassium hydride gives a mixture of eta-5-cpRu(NH2)(Cy2PCH2CH2PCy2), eta-5-cpRuH(Cy2PCH2CH2PCy2), and eta-cpRu2H(mu-Cy2PCH2CH2PCy)2. Treating [eta-5-cpRu(NH2C8H17-1)(Cy2PCH2CH2PCy2)]+ with potassium hydride gives eta-5-cpRu(NH2)(Cy2PCH2CH2PCy2) and eta-5-cpRuH(Cy2PCH2CH2PCy2). The organic product is 1-octanenitrile. The compound [eta-5-cpRu(NH3)(PPh3)2]CF3SO3 crystallizes in the monoclinic space group P2(1)/n with a = 12.667 (1) angstrom, b = 14.356 (3) angstrom, c = 21.457 (4) angstrom, beta = 96.58 (1)-degrees, and Z = 4. The structure was refined to R = 0.034 and R(w) = 0.046 on the basis of 4815 unique reflections with I greater-than-or-equal-to 3.0-sigma(I) and 479 variables. The compound [eta-5-cpRu(NH2CMe3)(PPh3)(P(OMe)3)]CF3SO3 crystallizes in the monoclinic space group P2(1)/n with a = 10.366 (2) angstrom, b = 21.862 (2) angstrom, c = 15.371 (2) angstrom, beta = 92.33 (1)-degrees, and Z = 4. The structure was refined to R = 0.041 and R(w) = 0.063 on the basis of 4778 unique reflections with I greater-than-or-equal-to 3.0-sigma(I) and 415 variables. The compound [eta-5-cpRu(NH2C8H17-1)(Cy2PCH2CH2PCy2)]CF3SO3 crystallizes in the rhombohedral space group R3BAR with a = 40.907 (3) angstrom, c = 13.621 (2) angstrom, and Z = 18. The structure was refined to R = 0.048 and R(w) = 0.066 on the basis of 4111 unique reflections with I greater-than-or-equal-to 3.0-sigma(I) and 435 variables. The compound [eta-5-cpRu(CO)(Cy2PCH2CH2PCy2)]CF3SO3 crystallizes in the monoclinic space group P2(1)/n with a = 14.940 (5) angstrom, b = 15.394 (10) angstrom, c = 18.242 (4) angstrom, beta = 97.63 (2)-degrees, and Z = 4. The structure defined to R = 0.054 and R(w) = 0.078 on the basis of 4657 unique reflections with I greater-than-or-equal-to 3.0-sigma(I) and 411 variables.