Oxidation of Co2+ by diphenyl diselenide in the presence of cis-[PPN][Mn(CO)4(SePh)2], followed by carbonyl shift from Mn(I) to Co(III) and a benzeneselenolate group rearranging to bridge two metals, led directly to the thermally unstable (CO)4Mn(μ-SePh)2Co(CO)(μ-SePh) 3Mn(CO)3. Dropwise addition of [PPN][SePh] to the neutral (CO)4Mn(μ-SePh)2Co(CO)(μ-SePh) 3Mn(CO)3 resulted in formation of a linear trinuclear complex possessing a hexaselenolatecobalt(III) core, [PPN][(CO)3Mn(μ-SePh)3Co(μ-SePh) 3Mn(CO)3]. This complex crystallized in the triclinic space group P1̄ with a = 10.878(1) Å = 15.095(2) Å, c = 25.372(4) Å, α = 95.04(1)°, β= 95.00(1)°, γ = 91.52(2)°, V = 4132(2) Å3, and Z = 2; final R = 0.042 and Rw = 0.042. In contrast, the thermally unstable da-[PPN][Mn(CO)4(SeMe)2], which was reacted with Co(C104)2·6H2O and (MeSe)2 in THF under a nitrogen atmosphere, led to the isolation of the stable heterometallic selenolate (CO)4Mn(μ-SeMe)2Co(CO)(μ-SeMe) 3Mn(CO)3. Crystal data: monoclinic space group C2/c, a = 28.41.3(7) Å, b = 11.091(3) Å, c = 22.849(6) Å, β= 125.06(3)°, V = 5894(3) Å3, and Z = 8; final R = 0.047 and Rw = 0.048. The results indicated that the distinct electronic effects between methaneselenolate and benzeneselenolate play a key role in stabilizing the neutral Mn(I)-Co(III)-Mn(I)-selenolate complexes.
|Number of pages||5|
|Publication status||Published - 1997 Dec 1|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry