The infrared spectra and theoretical calculations of frequencies of fac-tricarbonyl octahedral complexes of manganese(I)

Reaction chemistry of tricarbonyl-η5-pentadienylmanganese: Straightforward synthesis of stable manganese carbonyl terminal thiolates and a dinuclear bis(ethylenediaminyl) complex

“…Complexes (2)e(6) are octahedral and possess a C s point group that gives rise to three carbonyl stretching modes (2A 0 þ A 00 ) in their IR spectra [8]. It can be concluded from IR data of complexes (2)e(6) (see Experimental) that there is no distinct general correlation between the electronic or steric properties of the thiolates and their n(CO) bands.…”

“…Complexes fac-Mn(CO) 3 (SR)(H 2 NCH 2 CH 2 NH 2 -k 2 -N,N 0 ), R ¼ Ph (7) and C 6 F 5 (8) Reaction of pentadienyl complex (1) with mercaptans RSH, R ¼ Ph and C 6 F 5 , in the presence of ethylenediamine gave (7) and (8) as shown in Scheme 5. (1)…”

“…with similar shape and wave numbers to those of (2)e(6) (see Table 1); notwithstanding, one perceptible difference is observed in the wave number of the band assigned to the A 00 stretching mode (1919 and 1926 cm À1 , for (7) and (8), resp.). It has been proposed that this band stems from the out-of-phase vibration (antisymmetric with respect to the mirror plane of the molecule) of equatorial carbonyls [8] that in (7) and (8) are trans to the ethylenediamine eNH 2 groups. This fact suggests that ethylenediamine donates more electron density to the manganese than it can receive, if at all, rendering the A 00 mode n(CO) band to appear at lower wave number than in (2)e (6).…”

“…So, formation of (7) takes place in 2 h by (7); Mn(1)eP(1) 2.3095 (7). S(1)eMn(1)eC (7) 173.90 (8), C(9)eMn(1)eP (1) 178.55 (8), C(8)e Mn(1)eP (2) 174.18 (8), C(1)eS (1)eMn (1) 113.02 (9), P(1)eMn(1)eP (2) (1); (1) 1.813(3); Mn(1)eC (2) 1.790 (3); Mn(1)eS (1) 2.4098(9); Mn(1)eP(1) 2.3194 (8). S(1)eMn (1)eC (2) 177.97(10), C(1)eMn (1)eP (1) 174.10 (9), C(3)eMn(1)eP (2) 169.59 (10), C(6)eS (1)eMn (1) 110.93 (9), P(1)eMn (1)eP (2) 84.52(3).…”

Synthetic and structural studies of phosphorus carbonyl rhenacycles containing the tetraphenyldithioimidodiphosphinato ligand

“…The IR spectra of (1)e(4) are similar: all show three bands (in CH 2 Cl 2 solution) in the n(CO) carbonyl region corresponding to the 2A 0 þ A 00 vibrational modes [8] arising from the carbonyl groups' local symmetry with a C s point group assigned to mononuclear complexes with fac disposition involving both sulfur atoms [9]. Coordination of the dithioimidodiphosphinato moiety of complexes (1)e(4) in deprotonated form is evident from the n(P 2 N) vibrations (see Experimental) since the protonated form shows n(P 2 NH) at approx.…”