Synthesis and structural studies of cationic bis- and tris(pyrazol-1-yl)methane acyl and methyl complexes of ruthenium(II): Localization of the counterion in solution by NOESY NMR spectroscopy

Macchioni A.; Cardaci G.; Cruciani G.; Foresti E. Sabatino P.; Zuccaccia C.; Bellachioma G.

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Synthesis and structural studies of cationic bis- and tris(pyrazol-1-yl)methane acyl and methyl complexes of ruthenium(II): Localization of the counterion in solution by NOESY NMR spectroscopy

机译：钌（II）的阳离子双和三（吡唑-1-基）甲烷酰基和甲基络合物的合成和结构研究：NOESY NMR光谱法确定反离子在溶液中的定位

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Complex fac-Ru(PMe3)(CO)(3)(Me)I (1) reacts with tris- and bis(pyrazol-1-yl)methane, in the presence of NdBPh4, affording cis-[Ru(PMe3)(CO)(2)(COMe)(eta(2)-pz(3)-CH)]BPh4 (2) and cis-[Ru(PMe3)(CO)(2)(COMe)(pz(2)-CH2)]BPh4 (4), respectively. Complexes 2 and 4 decarbonylate leading to [Ru(PMe3)(CO)(COMe)(eta(3)-pz(3)-CH)]BPh4 (3) and a mixture of three methyl stereoisomers of cis-[Ru(PMe3)(CO)(2)(Me)(pz(2)-CH2)]BPh4 (5-7), respectively. The byproduct of the synthesis of 1, fac,cis-Ru(PMe3)(CO)(3)(I)(2) (8), reacts with bis(pyrazol-1-yl)methane affording cis-[Ru(PMe3)(CO)(2)(I)(pz(2)-CH2)]BPh4 (9). The stereochemistry of the complexes, the dynamic processes existing between them, and the interionic structures of all of the cationic complexes were investigated by the phase-sensitive H-1 NOESY NMR spectra in CD2Cl2. The solid-state crystal structure of 4, obtained by single-crystal X-ray studies, was compared from the intramolecular and interionic point of views with that in solution with the help of 3-21G* ab initio and AMI-SM2 semiempirical quantum mechanical and docking mechanic calculations. In particular, the differences of interaction energy of-the six solid-state ion pairs determined by the cation and the six symmetry-related anions surrounding it were estimated. The main result is that the averaged preferred position of the counterion in solution corresponds to the ion-pair electrostatically (Delta E-el > 2.5 kcal/mol) and "sterically" (Delta E-st > 3.7 kcal/mol) favored in the solid state. [References: 32]

机译：复杂的fac-Ru（PMe3）（CO）（3）（Me）I（1）在NdBPh4存在下与三和双（吡唑-1-基）甲烷反应，得到顺式[Ru（PMe3）（ CO）（2）（COMe）（eta（2）-pz（3）-CH）] BPh4（2）和顺式-[Ru（PMe3）（CO）（2）（COMe）（pz（2）-CH2 ）] BPh4（4）。配合物2和4脱羰形成[Ru（PMe3）（CO）（COMe）（eta（3）-pz（3）-CH）] BPh4（3）和顺式[Ru（PMe3）的三种甲基立体异构体的混合物）（CO）（2）（Me）（pz（2）-CH2）] BPh4（5-7）。 1，fac，cis-Ru（PMe3）（CO）（3）（I）（2）（8）的合成副产物与双（pyrazol-1-yl）甲烷反应得到cis- [Ru（PMe3））（CO）（2）（I）（pz（2）-CH2）] BPh4（9）。通过CD2Cl2中的相敏H-1 NOESY NMR光谱研究了配合物的立体化学，它们之间存在的动力学过程以及所有阳离子配合物的离子间结构。通过分子内和离子间的观点，比较了通过单晶X射线研究获得的4的固态晶体结构，并借助3-21G *从头算和AMI-SM2半经验量子力学比较了溶液中的固态晶体结构。和对接机械计算。特别地，估计了由阳离子和围绕它的六个对称相关阴离子确定的六个固态离子对的相互作用能的差。主要结果是抗衡离子在溶液中的平均优先位置对应于静电对中离子对（Delta E-el> 2.5 kcal / mol）和“空间”离子对（Delta E-st> 3.7 kcal / mol）。固体状态。 [参考：32]

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《Organometallics》 |1998年第25期|共8页
作者
Macchioni A.; Cardaci G.; Cruciani G.; Foresti E. Sabatino P.; Zuccaccia C.; Bellachioma G.;
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正文语种 eng
中图分类有机化学;有机质材料;
关键词
X-ray structure; Ion-pair; Olefin polymerization; Interionic contacts; Acetyl complexes; Lewis-acids; Catalysts; Lithium; Hoesy; Polyazolylmethanes;

机译：X射线结构;离子对;烯烃聚合;离子接触;乙酰基络合物;路易斯酸;催化剂;锂;Hoesy;聚唑基甲烷;

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1. Synthesis and structural studies of cationic bis- and tris(pyrazol-1-yl)methane acyl and methyl complexes of ruthenium(II): Localization of the counterion in solution by NOESY NMR spectroscopy [J] . Macchioni A., Cardaci G., Cruciani G., Organometallics . 1998,第25期

机译：钌（II）的阳离子双和三（吡唑-1-基）甲烷酰基和甲基络合物的合成和结构研究：NOESY NMR光谱法确定反离子在溶液中的定位
2. Synthesis and structural features of new ruthenium(ii) complexes containing the scorpionate ligands tris(pyrazol-1-yl)methanesulfonate (Tpms) and tris(pyrazol-1-yl)methane (Tpm) [J] . Miguel S., Diez J., Gamasa M.P., European journal of inorganic chemistry . 2011,第30期

机译：含有蝎子配体三（吡唑-1-基）甲磺酸盐（Tpms）和三（吡唑-1-基）甲烷（Tpm）的新钌（ii）配合物的合成和结构特征
3. Cationic acetyl complexes of iron(II) and ruthenium(II) bearing neutral N,O ligands: Synthesis, characterization, and interionic solution structure by NOESY NMR spectroscopy [J] . Bellachioma G., Gramlich V., Macchioni A., Organometallics . 1998,第23期

机译：具有中性N，O配体的铁（II）和钌（II）的阳离子乙酰配合物：NOESY NMR光谱法的合成，表征和离子间溶液结构
4. RUTHENIUM(II) TRIS-BIPYRIDINE COMPLEXES WITH A 60FULLERENE LIGAND: SYNTHESIS AND PROPERTIES [C] . Michele Maggini, Enzo Menna, Giorgia Possamai, International Symposium on Fullerenes, Nanotubes, and Carbon Nanoclusters, Mar, 25-29, 2001, Washington, D.C. . 2001

机译：60富勒烯配体的钌（II）三联吡啶络合物的合成与性能
5. IRON AND RUTHENIUM COMPLEXES POSSESSING UNUSUAL ELECTRONIC PROPERTIES. PART I: SYNTHESIS AND SPIN STATE STUDIES OF GAMMA-SUBSTITUTED TRIS(BETA-DIKETONATO)IRON(III) COMPLEXES AND THEIR BETA-KETOIMINE ANALOGUES DERIVED FROM TRIETHYLENETETRAMINE. PART II: A DIRECT MEASUREMENT OF DYNAMIC SPIN INTERCONVERSION RATES IN THE SPIN EQUILIBRIUM PROTEIN FERRIC MYOGLOBIN HYDROXIDE. PART III: SYNTHESIS, PHOTOEMISSION, AND ELECTROCHEMICAL STUDIES OF. [D] . DOSE, ERIC VON. 1978

机译：铁和钌络合物具有异常的电子特性。第一部分：γ-取代的三（三乙酮）铁（III）配合物及其三乙胺丁胺类似物的β-酮亚胺类似物的合成和自旋态研究。第二部分：纺丝平衡蛋白三水合肌红蛋白中动态纺丝互变速率的直接测量。第三部分：的合成，光生化和电化学研究。
6. Synthesis Characterization and Solution Chemistry oftrans-Indazoliumtetrachlorobis(Indazole)Ruthenate(III) a NewAnticancer Ruthenium Complex. IR UV NMR HPLC Investigations andAntitumor Activity. Crystal Structures of trans-1-Methyl-Indazoliumtetrachlorobis-(1-Methylindazole)Ruthenate(III)and its Hydrolysis Product trans-Monoaquatrichlorobis-(1-Methylindazole)-Ruthenate(III) [O] . Kari-Georg Lipponer, Ellen Vogel, Bernhard K. Keppler 1996

机译：of的合成表征与溶液化学。一种新型的反式吲哚四氯双（吲唑）钌（III）钌抗癌复合物。 IRUVNMRHPLC研究和抗肿瘤活性。反式-1-甲基-吲唑四氯双-（1-甲基吲唑）钌的晶体结构（III）及其水解产物反-季铵三氯-（1-甲基吲唑）-钌（III）
7. Synthesis and structural features of new ruthenium(II) complexes containing the scorpionate ligands tris(pyrazol-1-yl)methanesulfonate (Tpms) and tris(pyrazol-1-yl)methane (Tpm): Erratum [O] . Miguel Fernández Sara, Díez Viñuela Josefina Soledad, Gamasa Bandrés María Pilar, 2011

机译：含有蝎子配体三（吡唑-1-基）甲磺酸盐（Tpms）和三（吡唑-1-基）甲烷（Tpm）的新钌（II）配合物的合成和结构特征：勘误
8. Moessbauer Spectroscopy Study of Tris (2-Pyridinalimine) and Tris (2-Pyridilketoimine)-Iron(II) Complexes [R] . Saitovitch, E. B., de Souza, N. G., Vichi, E. J. S. 1977

机译：三（2-吡啶亚胺）和三（2-吡啶酮亚胺） - 铁（II）配合物的穆斯堡尔光谱研究

Synthesis and structural studies of cationic bis- and tris(pyrazol-1-yl)methane acyl and methyl complexes of ruthenium(II): Localization of the counterion in solution by NOESY NMR spectroscopy

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