| Research Abstract |
Reaction of[n-C_4H_9]_4N]_2[Mo_2O_7], Cp^*TiCl_3,and [n-C_4H_9)_4N]OH in CH_3CN yields[(n-C_4H_9)_4N]_3[Cp^*TiMo_5O_<18>]・CH_3CN [a=12.863(4) Å,b=26.608(6) Å,c=24.534(4) Å,β=103.88(2)°,Z=4,space group P2_1/c (No.14)]. Similar reaction without[(n-C_4H_9)_4N]OH yields monoprotonated complex[n-C_4H_9)_4N]_2[HCp^*TiMo_5O_<18>], where, according to a single-crystal x-ray diffraction study[a=19.9550(4) Å,b=25.5420(8) Å,c=11.8820(3) Å,β=100.31(2)°,Z=4,space group P2_1/n (No.14)], the anion is protonated at one of OMo_2 doubly-bridging oxygens. Reaction of[On-C_4H_9]_4N]_2[HCp^*TiMo_5O_<18>] with CCl_3COOH in CHCl_3 followed by crystallization from CH_3CN/Et_2O yields diprotonated[(n-C_4H_9)_4N][H_2Cp^*TiMo_5O_<18>]・1/4(C_2H_5)_2O, which, according to a single-crystal x-ray diffraction study[a=12.319(2) Å,b=16.105(3) Å,c=12.001(2) Å,a=110.74(1)°,β=100.31(2)°,γ=82.777(5),Z=2,space group P1^^-(No.2)], contains hydrogen-bonded dimers of[H_2Cp^*TiMo_5O_<18>]^-ions. The[Cp^*TiMo_5O_<18>]^<3^-> is basic enough to form stable organometallic adducts like[η-C_8H_<12>)Ir(Cp^*TiMo_5O_<18>]^<2^-> and[(η-C_8H_<14>)Rh(Cp^*TiMo_5O_<18>]^<2^->.
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