Mass spectra of organometallic compounds —VII; Organonitrogen derivatives of metal carbonyls

The positive‐ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC 5 H 4 CH 2 Fe(CO) 2 C 5 H 5 , NC 5 H 4 CH 2 COMo(CO) 2 C 5 H 5 , NC 5 H 4 CH 2 W(CO) 3 C 5 H 5 , NC 5 H 4 CH 2 COMn(CO) 4 , C 5 H 10 NCH 2 CH 2 Fe(CO) 2 C 5 H 5 , (CH 3 ) 2 NCH 2 CH 2 COFeCOC 5 H 5 and (CH 3 ) 2 NCH 2 CH 2 COMn(CO) 4 obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C 5 H 5 Mo(CO) 3 CH 2 NCO; (iii) The arylazomolybdenum derivatives RN 2 Mo(CO) 2 C 5 H 5 (R phenyl, p ‐tolyl, or p ‐anisyl); (iv) The compound (C 6 H 5 N) 2 COFe 2 (CO) 6 obtained from Fe 3 (CO) 12 and phenyl isocyanate; (v) The N,N,N′,N′‐tetramethylethylenediamine complex (CH 3 ) 2 NCH 2 CH 2 N(CH 3 ) 2 W(CO) 4 . Further examples of eliminations of hydrogen, CO, and C 2 H 2 fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC 5 H 4 CH 2 MC 5 H 5 ] + to give the ions [(C 5 H 5 ) 2 M] + (M Fe, Mo and W); (ii) Conversion of C 5 H 5 Mo(CO) 3 CH 2 NCO to C 5 H 5 Mo(CO) 2 CH 2 NCO within the mass spectrometer; (iii) Elimination of N 2 from [RN 2 MoC 5 H 5 ] + to give [RMoC 5 H 5 ] + ; (iv) Novel eliminations of HNCO, FeNCO, and C 6 H 5 NC fragments in the mass spectrum of (C 6 H 5 N) 2 COFe 2 (CO) 6 ; (v) Facile dehydrogenation of the N,N,N′,‐N′‐tetramethylethylenediamine ligand in the complex (CH 3 ) 2 NCH 2 CH 2 N(CH 3 ) 2 W(CO) 4 .