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.
Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221-0172, USA. ault@email.uc.edu
Bruce S
BS
Ault
Thomas M
TM
Becker
Guang Qing
GQ
Li
Milton
M
Orchin
D008024:Ligands; D008345:Manganese / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D008024:Ligands; D009930:Organic Chemicals; D008345:Manganese