TY - JOUR
T1 - 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
T2 - Factors Affecting Bending in Two-Coordinate Metal Complexes with Aryl-Substituted Ligands
AU - Ellison, Jeffrey J.
AU - Ruhlandt-Senge, Karin
AU - Hope, Håkon H.
AU - Power, Philip P.
PY - 1995/9/1
Y1 - 1995/9/1
N2 - 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.
AB - 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.
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U2 - 10.1021/ic00105a012
DO - 10.1021/ic00105a012
M3 - Article
AN - SCOPUS:0002843157
SN - 0020-1669
VL - 34
SP - 49
EP - 54
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 1
ER -