Helpful correlations to estimate the pK(a) of coordinated HNO: a potential-pH exploration in a pendant-arm cyclam-based ruthenium nitroxyl

Perdomenico Julian; Ruiz Mariano M.; Osa Codesido Nicolas; De Candia Ariel G.; Marcolongo Juan P.; Slep Leonardo D.

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Helpful correlations to estimate the pK(a) of coordinated HNO: a potential-pH exploration in a pendant-arm cyclam-based ruthenium nitroxyl

机译：有用的相关性来估计协调的HNO的PK（a）：侧臂循环钌钌中的潜在-PP探索硝基

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The acid-base speciation of coordinated azanone (HNO) remains a highly relevant topic in bioinorganic chemistry. Ruthenium nitroxyl complexes with sufficient robustness towards ligand loss have gained significance as operating platforms to delve into such studies. In this work, we revisit an octahedral {RuNO}(6) complex containing the cyclam-based pentadentate ligand L-py = 1-(pyridine-2-ylmethyl)-1,4,8,11-tetraazacyclotetradecane and explore the thermodynamic and spectroscopic aspects of its reduced states in aqueous media. Upon in situ electro-generation of the bound HNO moiety, we have undertaken different strategies to determine both its acidity and electrochemical properties. This robust HNO complex does not undergo deprotonation in a wide pH range. We have found pK(a) ([Ru(L-py)(HNO)](2+)) = 13.0 +/- 0.1 and . There are indications that pK(a) (HNO) values in several ruthenium-based species correlate with the redox potential associated with the {RuNO}(6,7) and {RuNO}(7,8) couples. The present pK(a) extends the range of acidity of bound HNO to more than five pH units, confirming a remarkable sensitivity to the nature of the coordination sphere. This result lays new foundations to continue rational ligand design that may contribute to a better understanding of the different biological roles of both HNO and NO- by investigating key chemical aspects of model complexes.

机译：配位氮杂酮（HNO）的酸碱形态分析仍然是生物无机化学中一个高度相关的话题。对配体损失具有足够鲁棒性的钌-硝基配合物作为深入研究此类研究的操作平台具有重要意义。在这项工作中，我们重新考察了一种八面体{RuNO}（6）络合物，该络合物含有环胺基五齿配体L-py=1-（吡啶-2-基甲基）-1,4,8,11-四氮杂环十四烷，并探索了其在水介质中还原态的热力学和光谱方面。在原位生成结合的HNO部分后，我们采取了不同的策略来确定其酸性和电化学性质。这种坚固的HNO络合物在很宽的pH范围内不会发生脱质子。我们发现pK（a）（[Ru（L-py）（HNO）]（2+）=13.0+/-0.1和。有迹象表明，几种钌基物种的pK（a）（HNO）值与与{RuNO}（6,7）和{RuNO}（7,8）对相关的氧化还原电位相关。目前的pK（a）将结合HNO的酸度范围扩大到五个以上的pH单位，证实了对配位球性质的显著敏感性。这一结果为继续进行合理的配体设计奠定了新的基础，通过研究模型配合物的关键化学方面，有助于更好地理解HNO和NO的不同生物学作用。

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《Dalton transactions: An international journal of inorganic chemistry》 |2021年第5期|共10页
作者
Perdomenico Julian; Ruiz Mariano M.; Osa Codesido Nicolas; De Candia Ariel G.; Marcolongo Juan P.; Slep Leonardo D.;
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Univ Buenos Aires Fac Ciencias Exactas &

Nat Dept Quim Inorgan Analit &

Quim Fis Pabellon 2 Ciudad Univ C1428EHA Buenos Aires DF Argentina;

Univ Buenos Aires Fac Ciencias Exactas &

Nat Dept Quim Inorgan Analit &

Quim Fis Pabellon 2 Ciudad Univ C1428EHA Buenos Aires DF Argentina;

Univ Buenos Aires Fac Ciencias Exactas &

Nat Dept Quim Inorgan Analit &

Quim Fis Pabellon 2 Ciudad Univ C1428EHA Buenos Aires DF Argentina;

CIBION CONICET Ctr Invest Bionanociencias NMR Grp Polo Cient Tecnol Godoy Cruz 2320 C1425FQD Buenos Aires DF Argentina;

Univ Buenos Aires Fac Ciencias Exactas &

Nat Dept Quim Inorgan Analit &

Quim Fis Pabellon 2 Ciudad Univ C1428EHA Buenos Aires DF Argentina;

Univ Buenos Aires Fac Ciencias Exactas &

Nat Dept Quim Inorgan Analit &

Quim Fis Pabellon 2 Ciudad Univ C1428EHA Buenos Aires DF Argentina;

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正文语种 eng
中图分类化学;无机化学;
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1. Nitrosyl-Centered Redox and Acid?Base Interconversions in [Ru(Me_3[9]aneN_3)(bpy)(NO)]~(3,2,1+). The pK_a of HNO for its Nitroxyl Derivative in Aqueous Solution [J] . Nicola?s Osa Codesido, Thomas Weyhermu?ller, Jose? A. Olabe, Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2014,第2期

机译：[Ru（Me_3 [9] aneN_3）（bpy）（NO）]〜（3,2,1+）中亚硝基中心的氧化还原和酸碱互变。水溶液中HNO的HNO的pK_a
2. Remarkable Changes of the Acidity of Bound Nitroxyl (HNO) in the [Ru(Me-3[9]aneN(3))(L-2)(NO)](n+) Family (n=1-3). Systematic Structural and Chemical Exploration and Bioinorganic Chemistry Implications [J] . Levin Natalia, Osa Codesido Nicolas, Pablo Marcolongo Juan, Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2018,第19期

机译：[Ru（ME-3 [9] AneN（3））（L-2）（NO）]（N +）族（N = 1-3）中，[Ru（Me-3 [9] AneN（3））（N +）]（n = 1-3）中结合的硝红氧基（HNO）的酸度显着变化。系统的结构和化学探索和生物有机化学意义
3. Correlation of Relaxivity with Coordination Number in Six-, Seven-, and Eight-Coordinate Mn(II) Complexes of Pendant-Arm Cyclen Derivatives [J] . Wang S, Westmoreland TD Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2009,第2期

机译：悬臂臂式周期数衍生物的六，七和八坐标Mn（II）配合物中弛豫度与配位数的相关性
4. Correlation of Relaxivity with Coordination Number in Six- Seven- and Eight-Coordinate Mn(II) Complexes of Pendant-Arm Cyclen Derivatives [O] . Sen Wang, T. David Westmoreland -1

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Helpful correlations to estimate the pK(a) of coordinated HNO: a potential-pH exploration in a pendant-arm cyclam-based ruthenium nitroxyl

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