Ru(II)-hydride-trop complexes: X-ray single-crystal determination and quantum-chemical calculations.

IF 0.8 4区 化学 Acta crystallographica. Section C, Crystal structure communications Pub Date : 2013-12-15 Epub Date: 2013-11-08 DOI:10.1107/S0108270113024505
Gustavo Santiso-Quinones, Rafael Rodriguez-Lugo, Vittorio Sacchetti, Hansjörg Grützmacher
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引用次数: 2

Abstract

As part of our search for catalytically active Ru(II)-hydride complexes, we have synthesized and crystallographically characterized three different ruthenium species, namely dihydrido[(SR)-(10,11-η)-N-(pyridin-2-ylmethyl-κN)-5H-dibenzo[a,d]cyclohepten-5-amine](triphenylphosphane-κP)ruthenium(II) tetrahydrofuran monosolvate, [RuH2(C21H18N2)(C18H15P)]·C4H8O or (SR)-[Ru(II)(H)2{N-(pyridin-2-ylmethyl)tropNH}(PPh3)]·THF, (1), chlorido{(1SR,2RS)-N,N'-bis[(10,11-η)-5H-dibenzo[a,d]cyclohepten-5-amine]ethane-1,2-diamine-κ(2)N,N'}hydridoruthenium(II) dimethoxyethane hemisolvate, [RuClH(C32H28N2)]·0.5C4H10O2 or (1SR,2RS)-[Ru(II)(H)(Cl){tropNH(CH2)2HNtrop}]·DME, (2), and chlorido{(1SR,2RS)-N,N'-bis[(10,11-η)-5H-dibenzo[a,d]cyclohepten-5-amine]propane-1,3-diamine-κ(2)N,N'}hydridoruthenium(II), [RuClH(C33H30N2)] or (1SR,2RS)-[Ru(II)(H)(Cl){tropNH(CH2)3HNtrop}], (3), where trop is 5H-dibenzo[a,d]cycloheptene. In all three complexes, the Ru(II) center resides in an octahedral coordination environment. For (1)-(3), the hydride atoms were located in a difference Fourier map and were refined freely. In solution, the (1)H NMR spectra of all species show the presence of the hydride resonance. Comparison with quantum-chemical calculations reveals that the crystallographic data sets are plausible. In every case, the prediction is in very good agreement with the observed X-ray data. Not only the observed geometry is predicted well but also the Ru-H(hydride) bond lengths are reproduced remarkably well. Complexes (1) and (2) crystallized in the triclinic P1 space group, while (3) crystallized in the tetragonal space group I4(1)/a. For (3), there is disorder of the axial ligands producing two isomers (in a 98.7:1.3 ratio). Details of the synthesis, characterization, X-ray analysis, and theoretical calculations for complexes (1)-(3) are presented.

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Ru(II)-氢化物-异构配合物:x射线单晶测定和量子化学计算。
作为我们寻找催化活性Ru(II)-氢化物配合物的一部分,我们合成并晶体表征了三种不同的钌物质,即二羟基[(SR)-(10,11-η)-N-(吡啶-2-基甲基-κN)- 5h -二苯并[a,d]环庚-5-胺](三苯膦-κ p)钌(II)四氢呋喃单溶剂化物,[RuH2(C21H18N2)(C18H15P)]·c4h80或(SR)-[Ru(II)(H)2{N-(吡啶-2-基甲基)tropNH}(PPh3)]·THF, (1),老chlorido{(1、2 rs) - N, N’bis((10 11 -η)5 h-dibenzo [a, d] cyclohepten-5-amine] ethane-1, 2-diamine -κ(2)N, N '} hydridoruthenium (II)乙二醇二甲醚hemisolvate, [RuClH (C32H28N2)]·0.5 c4h10o2或(1 sr, 2 rs) -[俄文(II) (H) (Cl) {tropNH (CH2) 2 hntrop}]·测距装置,(2),和chlorido {(1 sr, 2 rs) - N, N’bis((10 11 -η)5 h-dibenzo [a, d] cyclohepten-5-amine] propane-1, 3-diamine -κ(2)N, N '} hydridoruthenium (II), [RuClH (C33H30N2)或(1 sr, 2 rs) -[俄文(II) (H) (Cl) {tropNH (CH2) 3 hntrop}),(3),太是5 h-dibenzo [a, d] cycloheptene。在这三种配合物中,Ru(II)中心位于八面体配位环境中。对于(1)-(3),氢化物原子位于差分傅里叶图中,并进行了自由精炼。在溶液中,所有物质的(1)H NMR谱均表现出氢化物共振的存在。与量子化学计算的比较表明,晶体学数据集是可信的。在每一种情况下,预测都与观测到的x射线数据非常吻合。不仅可以很好地预测观察到的几何形状,而且可以很好地再现Ru-H(氢化物)键长。配合物(1)和(2)在三斜P1空间群中结晶,而(3)在I4(1)/a四方空间群中结晶。对于(3),轴向配体产生两个异构体(比例为98.7:1.3)存在无序性。详细的合成,表征,x射线分析,和理论计算的配合物(1)-(3)提出。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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期刊介绍: Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.
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