Synthesis and Characterization of the New Selenolate Ligand -SeC6H3-2, 6-Mes2 (Mes = C6H2-2, 4, 6-Me3) and Its Two-Coordinate Zinc and Manganese Derivatives: Factors Affecting Bending in Two-Coordinate Metal Complexes with Aryl-Substituted Ligands

Jeffrey J. Ellison, Karin Ruhlandt-Senge, Håkon H. Hope, Philip P. Power

Research output: Contribution to journalArticle

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Abstract

The synthesis and characterization of a novel sterically demanding selenol HSeC6H3-2, 6-Mes2, 1 (Mes = −C6H2-2, 4, 6-Me3), the corresponding diselenide, 2, and some of its metal derivatives are described. Solvated and unsolvated zinc selenolates were prepared by the treatment of the amide Zn{N(SiMe3)2}2 in hexane with 2 equiv of the bulky selenol, 1. Crystallization from hexane produces monomelic Zn(SeC6H3-2, 6-Mes2)2, 3, while crystallization from tetrahydrofuran results in the monomeric adduct Zn(SeC6H3-2, 6-Mes2)2(THF), 4. Treatment of Mn{N(SiMe3)2}2 with 2 equiv of 1 and crystallization from methylene chloride yields Mn(SeC6H3-2, 6-Mes2)2’2CH2Cl2, 5•2CH2C12. The synthesis and structure determination of [Mn(SeMes)2THF]2′4PhMe (Mes = −C6H2-2, 4, 6-t-Bu3), 6, were also undertaken to compare the steric properties of the −SeC6H3-2, 6-Mes2 and -SeMes ligands. The compounds 1–5 were characterized by IR and 1H NMR spectroscopy, and 1–4 were also characterized by 77Se NMR spectroscopy. The structures of 2–6 were determined by X-ray crystallography. In 3 the zinc has a crystallographically required linear coordination whereas the manganese atom in 5 has a bent geometry with a Se-Mn-Se angle of 119.9(1)°. In contrast, the structure of 6 is dimeric even in the presence of THF donor ligands. Crystal data with Mo Kα (λ= 0.710 69 Å) (2 and 5) or Cu Kα (λ = 1.541 78 Å) (3 and 4) radiation at 130 K: 2, a = 16.144(4) Å, b = 15.122(3) Å, c = 16.155(4) Å, β = 91.86(2)°, monoclinic, Z = 4, space group P21/n, R = 0.056; 3, a = 9.318(2) Å, b= 10.904(4) Å, c = 11.796(4) Å, α = 62.25(2)°, β = 73.76(2)°, γ = 68.92(2)°, triclinic, Z = 2, space group P1, R = 0.059; 4, a = 10.621(3) Å, b = 10.828(3) Å, c = 22.491(6) Å, α = 86.76(2)°, β = 85.20(2)°, γ = 60.57(2)°, triclinic, Z = 2, space group P1, R = 0.073; 5•2CH2Cl2, a = 20.061(5) Å, b = 14.705(5) Å, c = 15.781(5) Å, orthorhombic, Z = 8, space group Pccn, R = 0.063; 6–4PhMe, a = 19.000(8) Å, b= 19.626(6) Å, c = 27.687(7) Å, β = 98.18(5)°, Z = 4, space group P21/n, R = 0.086.

Original languageEnglish (US)
Pages (from-to)49-54
Number of pages6
JournalInorganic Chemistry
Volume34
Issue number1
DOIs
StatePublished - Sep 1 1995
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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