N,N,N ',N '-Tetrakis(2-pyridylmethyl)ethylenediamine and its analogues as hypodentate ligands. Synthesis and characterization of the rhodium(III), ruthenium(II), and palladium(II) complexes.
N,N,N ',N '-Tetrakis(2-pyridylmethyl)ethylenediamine and its analogues as hypodentate ligands. Synthesis and characterization of the rhodium(III), ruthenium(II), and palladium(II) complexes.
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N,N,N,N-四(2-吡啶基甲基)乙二胺及其类似物作为次齿配体。
DOI：
10.1021/ic0203264
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发表时间：
2002
影响因子：
4.6
通讯作者：
Y. Sasaki
中科院分区：
文献类型：
--
作者：
M. Sokolov;K. Umakoshi;Y. Sasaki
本文报道了Rh（Ⅲ）、Ru（Ⅱ）和Pd（Ⅱ）与N，N，N ′，N ′-四（2-吡啶甲基）乙二胺（tpen）及其类似物的配合物。RhCl（3）·nH（2）O与tpen的反应是缓慢的，并且允许分离三个连续取代步骤的产物：Rh（2）Cl（6）（tpen）（1）、cis-[RhCl（2）（eta（4）-tpen）]（+）（2）和[RhCl（eta（5）-tpen）]（2+）（3）。在乙腈中，反应停止于形成cis-[RhCl（2）（eta（4）-tpen）]（+）的步骤，而[RhCl（eta（5）-tpen）]（2+）是在乙醇中进一步反应的最终产物。不能获得完全螯合的[Rh（tpen）]（3+）。双乙酰丙酮合钯（Ⅱ），Pd（acac）（2），与tpen及其类似物，N，N，N ′，N ′-四（2-吡啶基甲基）-1，3-丙二胺（tptn）和N，N，N '，N'-四（2-吡啶基甲基）-（R）-1，2-丙二胺（R-tppn），分别得到[Pd（eta（4）-tpen）]（2+）（4）、[Pd（eta（4）-tppn）]（2+）（5）和[Pd（eta（4）-tptn）]（2+）（6）。在这些情况下，两个吡啶基臂保持不协调。从这些Pd（II）配合物在溶液中形成不稳定的Pd（III）配合物的电化学测量的基础上，建议。钌（Ⅲ）配合物RuCl（3）·nH（2）O被还原，得到完全配位的钌（Ⅱ）配合物[Ru（tpen）]（2+）（7）.在Ru（II）Cl（2）（二甲基亚砜）（4）与tpen的更直接的反应中获得了相同的产物。电化学研究表明，[7]（ClO（4））（2）（E（1/2）= 1.05 V vs Ag/AgCl）存在准可逆的[Ru（tpen）]（2+/3+）电对。测定了[2]（PF（6））·2CH（3）CN、[3]（PF（6））·CH（3）CN、[6]（ClO（4））（2）和[7]（ClO（4））（2）·0.5H（2）O的晶体结构。晶体数据：[2]（PF（6））.2CH（3）CN，单斜晶系，C2，a = 16.974（4）A，B = 8.064（3）A，c = 13.247（3）A，β = 106.37（2）度，V = 1739.9（8）A（3），Z = 2;[3]（PF（6））（2）.CH（3）CN，三斜晶系，P1，a = 11.430（1）A，B = 19.234（3）A，c = 8.101（1）A，α = 99.43（1）度，β = 93.89（1）度，γ = 80.10（1）度，[6]（ClO（4））（2），正交晶系，Pnna，a = 8.147（1）A，B = 25.57（1）A，c = 14.770（4）A，V = 3076（3）A（3），Z = 4;[7]（ClO（4））（2）.0.5H（2）O，单斜晶系，P2（1）/c，a = 10.046（7）A，B = 19.049（2）A，c = 15.696（3）A，β = 101.46（3）度，V = 2943（2）A（3），Z = 4。
New complexes of Rh(III), Ru(II), and Pd(II) with N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (tpen) and its analogues have been prepared. The reaction of RhCl(3).nH(2)O with tpen is slow and allows one to isolate the products of three consecutive substitution steps: Rh(2)Cl(6)(tpen) (1), cis-[RhCl(2)(eta(4)-tpen)](+) (2), and [RhCl(eta(5)-tpen)](2+) (3). In acetonitrile the reaction stops at the step of the formation of cis-[RhCl(2)(eta(4)-tpen)](+), whereas [RhCl(eta(5)-tpen)](2+) is the final product of the further reaction in ethanol. Fully chelated [Rh(tpen)](3+) could not be obtained. Bis(acetylacetonato)palladium(II), Pd(acac)(2), reacts with tpen and its analogues, N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-propanediamine (tptn) and N,N,N',N'-tetrakis(2-pyridylmethyl)-(R)-1,2-propylenediamine (R-tppn), to give [Pd(eta(4)-tpen)](2+) (4), [Pd(eta(4)-tppn)](2+) (5), and [Pd(eta(4)-tptn)](2+) (6), respectively. Two pyridyl arms remain uncoordinated in these cases. The formation of unstable Pd(III) complexes from these Pd(II) complexes in solution was suggested on the basis of electrochemical measurements. Ruthenium(III) trichloride, RuCl(3).nH(2)O, is reduced to give a Ru(II) complex with fully coordinated tpen, [Ru(tpen)](2+) (7). The same product was obtained in a more straightforward reaction of Ru(II)Cl(2)(dimethyl sulfoxide)(4) with tpen. Electrochemical studies showed a quasi-reversible [Ru(tpen)](2+/3+) couple for [7](ClO(4))(2) (E(1/2) = 1.05 V vs Ag/AgCl). Crystal structures of [2](PF(6)).2CH(3)CN, [3](PF(6))(2).CH(3)CN, [6](ClO(4))(2), and [7](ClO(4))(2).0.5H(2)O were determined. Crystal data: [2](PF(6)).2CH(3)CN, monoclinic, C2, a = 16.974(4) A, b = 8.064(3) A, c = 13.247(3) A, beta = 106.37(2) degrees, V = 1739.9(8) A(3), Z = 2; [3](PF(6))(2).CH(3)CN, triclinic, P1, a = 11.430(1) A, b = 19.234(3) A, c = 8.101(1) A, alpha = 99.43(1) degrees, beta = 93.89(1) degrees, gamma = 80.10(1) degrees, V = 1729.3(4) A(3), Z = 2; [6](ClO(4))(2), orthorhombic, Pnna, a = 8.147(1) A, b = 25.57(1) A, c = 14.770(4) A, V = 3076(3) A(3), Z = 4; [7](ClO(4))(2).0.5H(2)O, monoclinic, P2(1)/c, a = 10.046(7) A, b = 19.049(2) A, c = 15.696(3) A, beta = 101.46(3) degrees, V = 2943(2) A(3), Z = 4.