The infrared spectra and theoretical calculations of frequencies of fac-tricarbonyl octahedral complexes of manganese(I).
The carbonyl stretching frequencies in the infrared spectra of 38 fac-tricarbonyl octahedral complexes of manganese(I) prepared in this laboratory were determined. These complexes may be grouped into three types: (a) neutral complexes of the structure (CO)(3)Mn(P-P)Z where P-P represents depe, dppe, or dppp, and Z represents various anionic functional groups bonded to the manganese; (b) ionic complexes of the structure [(CO)(3)Mn(P-P)Z](+)BF(4)(-) where Z represents various neutral molecules possessing one phosphorous, nitrogen, or oxygen atom coordinated to the manganese; (c) complexes of the structure (CO)(3)Mn(pn)Z where the chelating pn represents 1,1-diphenylphosphino-2,2-dimethylaminoethane, Ph(2)PCH(2)CH(2)NMe(2). All of these complexes show three carbonyl stretching modes (2A' + A"). The effects on the frequencies of these modes induced by both the various Z groups and the various ligands are discussed. Theoretical calculations (B3LYP/6-31G) with optimization of the full molecule make it possible to distinguish between the three stretching modes and to make unambiguous assignments of appropriate symmetry species to each.
Ault
Bruce S
BS
Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221-0172, USA. ault@email.uc.edu
Becker
Thomas M
TM
Li
Guang Qing
GQ
Orchin
Milton
M
D008024:Ligands; D008345:Manganese / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D008024:Ligands; D009930:Organic Chemicals; D008345:Manganese