REACTIVITY AND STRUCTURE OF (ETA(6)-C6(CH3)6)MN(CO)2H - STABLE ALKYLRHENIUM ANALOGS

The reactivity of Mr'H (2; Mr' = (eta6-C6(CH3)6)Mn(CO)2) with protic a cids, Lewis bases, and transition-metal organometallics is reported. R eaction of 2 with triflic acid or HBF4.Et2O generates H-2 and [Mr'(S)] + (S = CH2Cl2, OEt2, CF3SO3-). Treatment of 2 with CpW(CO)3X (X = Cl, I), CpFe(CO)2X (X = Cl, I), and Mn(CO)5Br results in metathesis to giv e Mr'X and CPW(CO)3H, CpFe(CO)2H, and Mn(CO)5H, respectively. Reaction of 2 with [CpFe(CO)2]2 produces CpFe(CO)2H and the new complex Mr'Fe( CO)2Cp. The reaction of [Rr'CO]PF6 (Rr' = (eta6-C6(CH3)6)Re(CO)2) With (CH3)3NO and (n-Bu)4NCl results in the formation of Rr'Cl (5a). React ion of 5a with t-BuLi produces Rr'(C(CH3)3), while reaction with K(C2H 5)3BH yields Rr'C2H5. The structures of 2 and 5a, determined by single -crystal X-ray diffraction studies, are reported here. Compound 2 crys tallizes in the space group Pna2(1) with unit cell dimensions a = 11.9 18(l) angstrom, b = 10.826(2) angstrom, c = 10.465(1) angstrom, Z = 4, V = 1350.2 angstrom3, R1 = 0.042, and R2 = 0.043. Compound 5a crystal lizes in the space group Pbca with unit cell dimensions a = 13.689(0) angstrom, b = 13.573(0) angstrom, c = 15.298(0) angstrom, z = 8, V = 2 842.4 angstrom3, R1 = 0.085, and R2 = 0.18.