THERMAL AND PHOTOLYTIC SUBSTITUTION OF DIMANGANESE DECACARBONYL WITH TRIFLUOROPHOSPHINE

Under thermal conditions, the PF3 substitution of Mn2(CO)10 produces five different compounds: 1-Mn2(CO)9(PF3), 1,1ʹ-Mn2(CO)8(PF3)2, 1,2-Mn2(CO)8(PF3)2, 1,1ʹ,2-Mn2(CO)7(PF3)3, and 1,1ʹ,2,2ʹ-Mn2-(CO)6(PF3)4. Photolytic excitation results in the formation of four additional compounds. Substitution is rigorously limited to the replacement of four carbon monoxides, but that replacement is fairly readily achieved. Compounds are identified by using a combination of GC-MS,19F NMR, and IR. Back reaction of 1,1ʹ,2,2ʹ-Mn2(CO)6(PF3)4 with13CO produces only the previously observed PF3-substituted compounds having extensive label. Side products produced include the monometallic hydride series HMn(CO)5-x(PF3)x(x = 1–5), the hydrogen-bridged series Mn2(μ-H)(μ-PF2)(CO)8-x(PF3)x (x = 2–5), and the bisphosphido-bridged series Mn2(µ-PF2)2(CO)8-x(PF3)x (x = 2–7). © 1990, American Chemical Society. All rights reserved.