Unsaturation in binuclear iron trifluorophosphine carbonyl derivatives: comparison with binary iron carbonyls

作者：Gong, Shida; Wang, Chaoyang; Li, Qian Shu^*; Xie, Yaoming; King, R Bruce

来源：Journal of Coordination Chemistry, 2012, 65(14): 2459-2477.

DOI：10.1080/00958972.2012.696108

• Iron
• Trifluorophosphine
• Density functional theory
• Metal carbonyls

Bridging PF3 groups are obviously very unfavorable as indicated by their absence in Fe-2(CO)(n)(PF3)(2) (n = 7, 6, 5, 4) complexes optimized by density functional theory even though many such structures have one or more bridging CO groups. Except for some Fe-2(CO)(7)(PF3)(2) structures, the two terminal PF3 groups are bonded to different irons. Structures of the saturated Fe-2(CO)(7)(PF3)(2) having one, two, and three bridging or semibridging CO groups have similar energies suggesting a fluxional system. The lowest energy structures for the unsaturated Fe-2(CO)(n)(PF3)(2) (n = 6, 5, 4) derivatives are triplet spin-state structures. However, higher energy singlet Fe-2(CO)(n)(PF3)(2) (n = 6, 5, 4) structures are found having formal iron-iron multiple bonds and various combinations of bridging and terminal CO groups leading to the favored 18-electron configurations for iron. Most singlet Fe-2(CO)(n)(PF3)(2) (n = 6, 5, 4) structures are analogous to those of the previous studied Fe-2(CO)(n 2) structures.

• 出版日期2012
• 单位华南师范大学