Ruthenium Complexes of Substituted Hydrazine: New Solution- and Solid-State Binding Modes

Dabb SL; Messerle BA; Otting G; Wagler J; Willis A

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Ruthenium Complexes of Substituted Hydrazine: New Solution- and Solid-State Binding Modes

机译：取代肼的钌配合物：新的溶液和固态结合模式

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The methylhydrazine complex [Ru(NH2NHMe)(PyP)(2)]Cl(BPh4) (PyP = 1-[2-(diphenylphosphino)ethyl]-pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(BPh4)(2). The inethylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (eta(2)-) when the complex is in the solid state and end-on (eta(1)-) when the complex is in solution. The solid-state structure of [Ru(PyP)(2)-(NH2NHMe)]Cl(BPh4) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with N-15 at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH2 group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP)(2)(eta(1)-NH2NRR')]OSO2CF3 (in which R = H, R' = Ph, R = R' = Me and NRR' = NC5H10) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)- (OSO2CF3)(2) in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.

机译：甲基肼配合物[Ru（NH2NHMe）（PyP）（2）] Cl（BPh4）（PyP = 1- [2-（二苯基膦基乙基）乙基]-吡唑）是通过将甲基肼加入双金属配合物[Ru（mu- Cl）（PyP）（2）]（2）（BPh4）（2）。钌配合物的乙基肼配体具有两种不同的结合模式：当配合物处于固态时为侧向（eta（2）-），当配合物处于溶液中时为侧向（eta（1）-）。通过X射线晶体学测定[Ru（PyP）（2）-（NH2NHMe）] Cl（BPh4）的固态结构。使用N-15进行自然丰度的2D NMR光谱实验证实，在溶液中，甲基肼仅通过-NH2基团与金属中心键合，并且钌络合物保留八面体构象。通过以下方法原位形成肼配合物[RuCl（PyP）（2）（eta（1）-NH2NRR'）] OSO2CF3（其中R = H，R'= Ph，R = R'= Me并且NRR'= NC5H10）将苯肼，1,1-二甲基肼和N-氨基哌啶分别添加到双金属配合物[Ru（mu-Cl）（PyP）（2）]（2）-（OSO2CF3）（2）的二氯甲烷溶液中。这些钌取代的肼配合物与双金属原料以平衡混合物形式存在。

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《Chemistry: A European journal》 |2008年第32期|共8页
作者
Dabb SL; Messerle BA; Otting G; Wagler J; Willis A;
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正文语种 eng
中图分类化学;
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coordination modes; hydrazine; NMR spectroscopy; ruthenium; X-ray diffraction; TRANSITION-METAL-COMPLEXES; HETERONUCLEAR COUPLING-CONSTANTS; N-N BOND; BIS(HYDRAZINE) COMPLEXES; MOLECULAR-STRUCTURE; NMR EXPERIMENTS; CP-ASTERISK; LIGANDS; N-15; NITROGENASE;

机译：配位模式;肼;NMR光谱;钌;X射线衍射;过渡金属络合物;异核耦合常数;NN键;BIS（肼）络合物;分子结构;NMR实验;CP-ASTERISK;LIGANDS;N- 15;硝化酶;

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1. Ruthenium Complexes of Substituted Hydrazine: New Solution- and Solid-State Binding Modes [J] . Dabb SL, Messerle BA, Otting G, Chemistry: A European journal . 2008,第32期

机译：取代肼的钌配合物：新的溶液和固态结合模式
2. Synthesis, structures, and DNA and protein binding of ruthenium(II)-p-cymene complexes of substituted pyridylimidazo[1,5-a] pyridine: enhanced cytotoxicity of complexes of ligands appended with a carbazole moiety [J] . Khamrang Themmila, Kartikeyan Radhakrishnan, Velusamy Marappan, RSC Advances . 2016,第115期

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3. Synthesis, structures, and DNA and protein binding of ruthenium(ii)-p-cymene complexes of substituted pyridylimidazo[1,5-a]pyridine: enhanced cytotoxicity of complexes of ligands appended with a carbazole moiety [J] . Themmila Khamrang, Radhakrishnan Kartikeyan, Marappan Velusamy, RSC Advances . 2016,第115期

机译：取代吡啶基咪唑钌（II）-p-cymene络合物的合成，结构和DNA和蛋白质结合[1,5-a]吡啶：增强配体的配合物与咔唑部分的配合物的细胞毒性
4. Quantification of Bindings of Organometallic Ruthenium Complexes to Protein Thiols by Mass Spectrometry [C] . Yumiao Han, Yu Lin, Fuyi Wang ASMS Conference on Mass Spectrometry and Allied Topics . 2016

机译：用质谱法定量有机金属钌配合物与蛋白质硫醇的粘合
5. Substitutionally labile ruthenium(II) carbonyl chelating triphosphine complexes and studies on syn and anti isomers of chelating triphosphine ruthenium complexes. [D] . Blosser, Patrick Wayne. 1993

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6. Delta chirality ruthenium ‘light-switch’ complexes can bind in the minor groove of DNA with five different binding modes [O] . James P. Hall, Páraic M. Keane, Hanna Beer, 2016

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Ruthenium Complexes of Substituted Hydrazine: New Solution- and Solid-State Binding Modes

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