10-Vertex Manganese−Dicarbollide Complexes from a Monocarbon Precursor. Synthesis and Cluster Vertex Functionalization of [1-OH-2,2,2-(CO)3-closo-2,1,10-MnC2B7H8]−

Reaction between [NBun4][closo-1-CB7H8] and [Mn2(CO)10] in THF (THF = tetrahydrofuran) at reflux temperatures, or at room temperature with ultraviolet irradiation, followed by addition of [N(PPh3)2]Cl, affords the manganese−dicarbollide salt [N(PPh3)2][1-OH-2,2,2-(CO)3-closo-2,1,10-MnC2B7H8] (1). Addition of NOBF4 to 1 gives the neutral species [1-OH-2,2-(CO)2-2-NO-closo-2,1,10-MnC2B7H8] (2), which readily undergoes CO substitution with PEt3 in the presence of Me3NO to yield [1-OH-2-CO-2-NO-2-PEt3-closo-2,1,10-MnC2B7H8] (3). Protonation of 1 in the presence of dialkyl sulfides SR2 affords the neutral complexes [1-SR2-2,2,2-(CO)3-closo-2,1,10-MnC2B7H8] [R = Me (4); SR2 = S(CH2)4 (5); R = {CH2CH═CH2} (6)]; the synthesis of 5 is accompanied by formation of a boron-substituted relative, [1-OH-6-{S(CH2)4}-2,2,2-(CO)3-closo-2,1,10-MnC2B7H7] (7). Addition of Me3NO to 6 in CH2Cl2 produces the anions [1-(SCH2CH═CH2)-2,2,2-(CO)3-closo-2,1,10-MnC2B7H8]− and [1,2-σ:η2-(SCH2CH═CH2)-2,2-(CO)2-closo-2,1,10-MnC2B7H8]−, i...