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.
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.