An Approach to Heterometallic Complexes with Selenolate and Tellurolate Ligands: Crystal Structures of cis-[Mn(CO)4(SePh)2] -,[(CO)3Mn(μ-SeMe)3Mn(CO)3] -,(CO)4Mn(μ-TePh)2Co(CO)(μ-SePh) 3Mn(CO)3, and (CO)3Mn(μ-SePh)3 Fe(CO)3

Wen Feng Liaw, Chih Ynan Chuang, Way-Zen Lee, Chen Kang Lee, Gene Hsiang Lee, Shie Ming Peng

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33 Citations (Scopus)

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) Å3, and Z = 2; final R = 0.085 and Rw = 0.094. Thermolytic transformation of cis-[Mn(CO)4(SeMe)2]- to [(CO)3Mn(μ-SeMe)3Mn(CO)3]- was accomplished in high yield in THF at room temperature. Crystal data for [Na-18-crown-6-ether][(CO)3Mn(μ-SeMe)3Mn(CO) 3]: trigonal space group R3̄, a = 13.533(3) Å, c = 32.292(8) Å, V = 5122(2) Å3, Z = 6, R = 0.042, Rw = 0.041. Oxidation of Co2+ to Co3+ 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)4Mn(μ-TePh)2Co(CO)(μ-SePh) 3Mn(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) Å3, Z = 2, R = 0.040, Rw = 0.040. Addition of fac-[Fe(CO)3(SePh)3]- to fac-[Mn(CO)3(CH3CN)3]+ resulted in formation of (CO)3Mn(μ-SePh)3Fe(CO)3. This neutral heterometallic complex crystallized in monoclinic space group P21/n with a = 8.707(2) Å, b = 17.413(4) Å, c = 17.541(4) Å, β = 99.72(2)°, V = 2621(1) Å3, and Z = 4; final R = 0.033 and Rw = 0.030.

Original languageEnglish
Pages (from-to)2530-2537
Number of pages8
JournalInorganic Chemistry
Volume35
Issue number9
Publication statusPublished - 1996 Dec 1

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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