title: Binuclear homoleptic manganese carbonyls: Mn2(CO)x (x = 10, 9, 8, 7).
abstract: The unsaturated homoleptic manganese carbonyls Mn(2)(CO)(n)() (n = 7, 8, 9) are characterized by their equilibrium geometries, thermochemistry, and vibrational frequencies using methods from density functional theory (DFT). The computed metal-metal distances for global minima range from 3.01 A for the unbridged Mn(2)(CO)(10) with a Mn-Mn single bond to 2.14 A for a monobridged Mn(2)(CO)(7) formulated with a metal-metal quadruple bond. The global minimum for Mn(2)(CO)(9) has a four-electron bridging mu-eta(2)-CO group and a 2.96 A Mn-Mn distance suggestive of the single bond required for 18-electron configurations for both metal atoms. This structure is closely related to an experimentally realized structure for the isolated and structurally characterized stable phosphine complex [R(2)PCH(2)PR(2)](2)Mn(2)(CO)(4)(mu-eta(2)-CO). An unbridged (OC)(4)Mn-Mn(CO)(5) structure for Mn(2)(CO)(9) has only slightly (<6 kcal/mol) higher energy with a somewhat shorter metal-metal distance of 2.77 A. For Mn(2)(CO)(8) the lowest energy structure is a D(2)(d)() unbridged structure with a 2.36 A metal-metal distance suggesting the triple bond required for the favored 18-electron configuration for both metal atoms. However, the unbridged unsymmetrical (CO)(3)Mn-Mn(CO)(5) structure with a metal-metal bond distance of 2.40 A lies only 1 to 3 kcal/mol above this global minimum. The lowest energy structure of Mn(2)(CO)(7) is an unbridged C(s)() structure with a short metal-metal distance of 2.26 A. This is followed energetically by another C(s)() unbridged Mn(2)(CO)(7) structure with a somewhat longer metal-metal distance of 2.38 A.
authors.affiliation: Center for Computational Quantum Chemistry and Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
authors.forename: Yaoming
authors.initials: Y
authors.lastname: Xie
authors.forename: Jee Hwan
authors.initials: JH
authors.lastname: Jang
authors.forename: R Bruce
authors.initials: RB
authors.lastname: King
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer
mesh_terms: D018360:Crystallography, X-Ray; D007202:Indicators and Reagents; D017895:Manganese Compounds / Q000737:chemistry*; D008670:Metals / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics
chemical_list: D007202:Indicators and Reagents; D017895:Manganese Compounds; D008670:Metals