REACTIONS OF [(ETA-6-C6(CH3)6)MN(CO)2(ETA-1-SCHSCPH3)]BF4 - FAST-ATOM-BOMBARDMENT TANDEM MASS-SPECTROMETRY OF DITHIOFORMATE AND THIOFORMAMIDE COMPLEXES - CRYSTAL-STRUCTURE OF [(ETA-6-C6(CH3)6)MN(CO)2SCHNET2]+BF4-

The reaction of (eta-6-C6(CH3)6)Mn(CO)2SC(S)H (1) with Ph3C+BF4- affords the adduct [(eta-6-C6(CH3)6)Mn(CO)2SCHSCPh3]+BF4- (2). Subsequent reaction of 2 with the nucleophiles diethylamine (HNEt2), aniline (H2NPh), and tert-butylamine (H2N-t-Bu) produces [(eta-6-C6(CH3)6)Mn(CO)2SCHNEt2]+BF4- (3), [(eta-6-C6(CH3)6)Mn(CO)2SCHNHPh]+BF4- (4), and [(eta-6-C6(CH3)6) Mn(CO)2SCHNH-t-Bu]+BF4- (5), respectively. The mass spectra of 1-5 and [(eta-6-C6(CH3)6)Mn(CO)2]2(mu-2-eta-2-SC(S)H)]+ (6) have been investigated using fast atom bombardment tandem mass spectrometry (FAB-MS/MS). Structural characterization and fragmentation patterns are derived from the collision-induced dissociation tandem mass spectra. The C-N single-bond cleavage within the N-substituted thioformamides is observed. Compounds 2-5 were also characterized by FTIR, FAB-MS, and H-1 and C-13 NMR spectroscopies. Compound 3 crystallizes in a triclinic unit cell, space group P1BAR, with Z = 2 and rho(calc) = 1.39 g/cm3, with cell dimensions of a = 8.312 (6) angstrom, b = 12.303 (4) angstrom, c = 13.325 (6) angstrom, alpha = 61.14 (3)-degrees, beta = 74.69 (5)-degrees, gamma = 75.69 (4)-degrees, and V = 1138 (2) angstrom3, obtained by a least-squares fit to 21 orientation reflections. R values are R1 = 0.054 and R2 = 0.088 for 2475 reflections greater than 3-sigma above background, averaged from 4451 independent reflections that were used in the least-squares refinement.