Heterometallic Complexes with Selenolate Ligands: Crystal Structures of [(CO)(3)Mn(&mgr;-SePh)(3)Co(&mgr;-SePh)(3)Mn(CO)(3)](-), (CO)(4)Mn(&mgr;-SeMe)(2)Co(CO)(&mgr;-SeMe)(3)Mn(CO)(3), and [(CO)(3)Mn(&mgr;-SePh)(3)Mn(CO)(3)](-).
Oxidation of Co(2+) 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)(4)Mn(&mgr;-SePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3). Dropwise addition of [PPN][SePh] to the neutral (CO)(4)Mn(&mgr;-SePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3) resulted in formation of a linear trinuclear complex possessing a hexaselenolatecobalt(III) core, [PPN][(CO)(3)Mn(&mgr;-SePh)(3)Co(&mgr;-SePh)(3)Mn(CO)(3)]. This complex crystallized in the triclinic space group P&onemacr; with a = 10.878(1) Å, b = 15.095(2) Å, c = 25.372(4) Å, alpha = 95.04(1) degrees, beta = 95.00(1) degrees, gamma = 91.52(2) degrees, V = 4132(2) Å(3), and Z = 2; final R = 0.042 and R(w) = 0.042. In contrast, the thermally unstable cis-[PPN][Mn(CO)(4)(SeMe)(2)], which was reacted with Co(ClO(4))(2).6H(2)O and (MeSe)(2) in THF under a nitrogen atmosphere, led to the isolation of the stable heterometallic selenolate (CO)(4)Mn(&mgr;-SeMe)(2)Co(CO)(&mgr;-SeMe)(3)Mn(CO)(3). Crystal data: monoclinic space group C2/c, a = 28.413(7) Å, b = 11.091(3) Å, c = 22.849(6) Å, beta = 125.06(3) degrees, V = 5894(3) Å(3), and Z = 8; final R = 0.047 and R(w) = 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.
Liaw
Wen-Feng
WF
Departments of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan, and National Taiwan University, Taipei 10074, Taiwan.
Lee
Way-Zen
WZ
Wang
Chun-Yuan
CY
Lee
Gene-Hsiang
GH
Peng
Shie-Ming
SM