双（吡唑-1-基）乙酸酯作为铁化学中的三脚架异蝎形配体：铁（II）和铁（III）与bpza、bdmpza和bdtbpza配体配合物的合成与结构

Bis(pyrazol-1-yl)acetates as tripodal heteroscorpionate ligands in iron chemistry: syntheses and structures of iron(II) and iron(III) complexes with bpza, bdmpza, and bdtbpza ligands.

作者信息

Beck Alexander, Barth Alexander, Hübner Eike, Burzlaff Nicolai

机构信息

Fachbereich Chemie, Universität Konstanz, Fach M728, D-78457 Konstanz, Germany.

出版信息

Inorg Chem. 2003 Nov 3;42(22):7182-8. doi: 10.1021/ic034097c.

DOI:10.1021/ic034097c

PMID:14577787

Abstract

The molecular structure of the previously reported species "[Fe(bdtbpza)Cl]" has been revealed by X-ray structure determination to be a ferrous dimer Fe(bdtbpza)Cl (2c) [bdtbpza = bis(3,5-di-tert-butylpyrazol-1-yl)acetate]. The syntheses of ferrous 2:1 complexes [Fe(bpza)(2)] (3a) and [Fe(bdtbpza)(2)] (3c) as well as ferric 1:1 complexes [NEt(4)][Fe(bpza)Cl(3)] (4a) and [NEt(4)][Fe(bdmpza)Cl(3)] (4b) [bpza = bis(pyrazol-1-yl)acetate, bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] are reported. Complexes 3a, previously reported [Fe(bdmpza)(2)] (3b), and 3c are high-spin. No spin crossover to the low-spin state was observed in the temperature range of 5-350 K. 4a and 4b are synthesized in one step and in high yield from NEt(4)[Cl(3)FeOFeCl(3)]. 4a and 4b are iron(III) high-spin complexes. Crystallographic information: 2c (C(24)H(39)ClFeN(4)O(2).CH(2)Cl(2).CH(3)CN) is triclinic, P1, a = 12.171(16) A, b = 12.851(14) A, c = 13.390(13) A, alpha = 98.61(9) degrees, beta = 113.51(11) degrees, gamma = 108.10(5) degrees, Z = 2; 3a (C(8)H(7)Fe(0.5)N(4)O(2)) is monoclinic, P2(1)/n, a = 7.4784(19) A, b = 7.604(3) A, c = 16.196(4) A, beta = 95.397(9) degrees, Z = 4; 3c (C(24)H(39)Fe(0.5)N(4)O(2)) is monoclinic, P2(1)/n, a = 9.939(6) A, b = 18.161(10) A, c = 13.722(8) A, beta = 97.67(7) degrees, Z = 4; 4b (C(20)H(35)Cl(3)FeN(5)O(2)) is monoclinic, C2/c, a = 30.45(6) A, b = 12.33(2) A, c = 16.17(3) A, beta = 118.47(5) degrees, Z = 8.

摘要

通过X射线结构测定，先前报道的物种“[Fe(bdtbpza)Cl]”的分子结构被揭示为亚铁二聚体[Fe(bdtbpza)Cl]₂(2c) [bdtbpza = 双(3,5 - 二叔丁基吡唑 - 1 - 基)乙酸酯]。报道了亚铁2:1配合物Fe(bpza)₂和Fe(bdtbpza)₂以及铁(III) 1:1配合物[NEt₄]Fe(bpza)Cl₃和[NEt₄]Fe(bdmpza)Cl₃ [bpza = 双(吡唑 - 1 - 基)乙酸酯，bdmpza = 双(3,5 - 二甲基吡唑 - 1 - 基)乙酸酯]的合成。配合物3a、先前报道的Fe(bdmpza)₂和3c是高自旋的。在5 - 350 K的温度范围内未观察到向低自旋态的自旋交叉。4a和4b由[NEt₄]₂[Cl₃FeOFeCl₃]一步合成且产率高。4a和4b是铁(III)高自旋配合物。晶体学信息：2c (C₂₄H₃₉ClFeN₄O₂·CH₂Cl₂·CH₃CN)为三斜晶系，P1，a = 12.171(16) Å，b = 12.851(14) Å，c = 13.390(13) Å，α = 98.61(9)°，β = 113.51(11)°，γ = 108.10(5)°，Z = 2；3a (C₈H₇Fe₀.₅N₄O₂)为单斜晶系，P2₁/n，a = 7.4784(19) Å，b = 7.604(3) Å，c = 16.196(4) Å，β = 95.397(9)°，Z = 4；3c (C₂₄H₃₉Fe₀.₅N₄O₂)为单斜晶系，P2₁/n，a = 9.939(6) Å，b = 18.161(10) Å，c = 13.722(8) Å，β = 97.67(7)°，Z = 4；4b (C₂₀H₃₅Cl₃FeN₅O₂)为单斜晶系，C2/c，a = 30.45(6) Å，b = 12.33(2) Å，c = 16.17(3) Å，β = 118.47(5)°，Z = 8。