Stereospecific Ligand Substitutions in Manganese(I) Complexes
Resource
Chemische Berichte 128 (2): 151-155
Journal
Chemische Berichte
Pages
151-155
Date Issued
1995
Date
1995
Author(s)
Abstract
AbstractTreatment of fac?[(P2SPh?P,P')Mn(CO)3Br] and fac?[(PS2Ph?P,S)Mn(CO)3Br] [P2SPh: Z = PPh2; PS2Ph: Z = SPh in CH3C?(CH2PPh2)(CH2SPh)(CH2Z)] with silver hexafluorophosphate yields the �b3?tripodal manganese complexes [(P2SPh?P,P',S)Mn(CO)3]PF6 (7) and [(PS2Ph?P,S,S')Mn(CO)3]PF6 (9), respectively, whereas the reaction of CH3C(CH2PPh2)2?(CH2SH) with Mn(CO)5Br gives directly [CH3C(Ph2?PCH2)2(CH2S)?P,P',S]Mn(CO)3 (11). Both ionic complexes 7 and 9 undergo stereospecifically ligand substitution upon treatment with Br?, I?, N?3, SCN? and CN? to give syn?fac?[(P2SPh?P,P')Mn(CO)3X] and syn?fac?[(PS2Ph?P,S)Mn(CO)3X] (X = Br, I, SCN, N3, CN) respectively, but the neutral complex 11 fails to undergo such a substitution reaction with these ions. However, reaction of I? with the complex [(PSMe)?P,P',S]Mn(CO)3]BF4 (20) [P2SMe = CH3C(CH2?PPh2)2(CH2SCH3)), which is obtained from the S?alkylation of 11 with (CH3)3OBF4, affords syn?fac?[(P2SMe)?P,P']Mn(CO)3I (22s) exclusively. The possible reaction mechanism of this ligand substitution is discussed.
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journal article
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