ISSN:
0009-2940
Keywords:
Tripodal ligands
;
Phosphane ligands
;
Thioethers
;
Manganese complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Treatment 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 η3-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.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951280211
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