Abstract
Oxidative addition of diorganyl diselenides to the coordinatively unsaturated, low-valent transition-metal-carbonyl fragment [Mn(CO) 5 ] - produced cis-[Mn(CO) 4 (SeR) 2 ] - . The complex cis-[PPN][Mn(CO) 4 (SePh) 2 ] crystallized in triclinic space group P1̄ with a = 10.892(8) Å, b = 10.992(7) Å, c = 27.021(4) Å, α = 101.93(4)°, β = 89.79(5)°, γ = 116.94(5)°, V = 2807(3) Å 3 , and Z = 2; final R = 0.085 and R w = 0.094. Thermolytic transformation of cis-[Mn(CO) 4 (SeMe) 2 ] - to [(CO) 3 Mn(μ-SeMe) 3 Mn(CO) 3 ] - was accomplished in high yield in THF at room temperature. Crystal data for [Na-18-crown-6-ether][(CO) 3 Mn(μ-SeMe) 3 Mn(CO) 3 ]: trigonal space group R3̄, a = 13.533(3) Å, c = 32.292(8) Å, V = 5122(2) Å 3 , Z = 6, R = 0.042, R w = 0.041. Oxidation of Co 2+ to Co 3+ by diphenyl diselenide in the presence of chelating metallo ligands cis-[Mn(CO) 4 (SePh) 2 ] - and cis-[Mn(CO) 4 (TePh) 2 ] - , followed by a bezenselenolate ligand rearranging to bridge two metals and a labile carbonyl shift from Mn to Co, led directly to [(CO) 4 Mn(μ-TePh) 2 Co(CO)(μ-SePh) 3 Mn(CO) 3 ]. Crystal data: triclinic space group P1̄, a = 11.712(3) Å, b = 12.197(3) Å, c = 15.754(3) Å, α = 83.56(2)°, β = 76.13(2)°, γ = 72.69(2)°, V = 2083.8(7) Å 3 , Z = 2, R = 0.040, R w = 0.040. Addition of fac-[Fe(CO) 3 (SePh) 3 ] - to fac-[Mn(CO) 3 (CH 3 CN) 3 ] + resulted in formation of (CO) 3 Mn(μ-SePh) 3 Fe(CO) 3 . This neutral heterometallic complex crystallized in monoclinic space group P2 1 /n with a = 8.707(2) Å, b = 17.413(4) Å, c = 17.541(4) Å, β = 99.72(2)°, V = 2621(1) Å 3 , and Z = 4; final R = 0.033 and R w = 0.030.