Principles of structure, bonding, and reactivity for metal nitrosyl complexes

doi:10.1016/S0010-8545(00)80259-3

Coordination Chemistry Reviews

Volume 13, Issue 4, September 1974, Pages 339-406

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Unveiling the electronic and molecular structure of a trinuclear ruthenium cluster containing one nitrosyl ligand
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The understanding of the Ru-NO bond in Ru nitrosyl systems is of great interest due to the non-innocent nature of the NO ligand, and because of the ability of such compounds to release nitric oxide, an essential physiological regulator. The Ru-NO bond description can be even more complicated when it comes to polynuclear systems such as the $μ$ -oxo clusters of general formula [Ru₃O(CH₃COO)₆(L)₃]ⁿ, which can be electronically localized or delocalized themselves depending on the nature of the L ligands, or present unpaired electrons depending on the Ru ions oxidation state. Herein, we present a detailed electronic- and molecular-structure description of the [Ru₃O(CH₃COO)₆(py)₂NO]PF₆ (py = pyridine) cluster using multiconfigurational approaches and X-ray diffraction analysis. The X-ray data unveil a linear Ru–NO moiety with a Ru-NO angle of 180°. Although most linear {RuNO}⁶ complexes have been largely described as Ru^II–NO⁺, our valence bond-type analysis based on a CASSCF ground state wavefunction, with an active space comprised of 18 electrons and 16 orbitals, showed a predominance of the Ru^III–NO° configuration, with minor contributions from Ru^IV–NO^– and Ru^II–NO⁺. These findings provide a more precise framework to rationalize the electronic properties of trinuclear ruthenium nitrosyls, aiding the planning of new NO releasers based on those clusters.
Oxo-centered trinuclear ruthenium acetates: Structure and applications
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Polynuclear μ-oxo complexes are commonly observed for second and third row transition metals. This review is particularly interested in the μ₃-oxo-bridged ruthenium trinuclear clusters of general formula [Ru₃O(CH₃COO)₆(L)₃]ⁿ, where typically L are coordinating solvents, N-heterocyclic ligands, phosphines or small species such as CO, NO, and CN^–; and n = 0 or + 1. These molecules are very versatile coordination compounds, characterized by an absorption profile with high coverage of the ultraviolet and visible regions, depending on their formal charges, and rich multi-electron redox behavior, yielding, for example, electrochromic devices and sensors. More recently, innovative approaches allowed the community to explore previously unfathomable applications for this type of system, such as trypanocidal or anticancer agents. Besides their intrinsic characteristics, they have also been used as building blocks for extended structures, opening up a whole new range of options. This text invites the readers to a description, from a structural point of view, of monomeric and extended compounds obtained from the primary unit [Ru₃O(RCOO)₆]ⁿ, reported on the last 20 years. In addition, we present an overview of the compounds' applications, focusing on their use as catalysts, in the construction of devices, or as final acceptors of excitation energy and electrons in photoinduced processes. Finally, we address the newest application reported in the literature: their biological activities as an anticancer, trypanocidal, or vasorelaxant agent and their interactions with target biomolecules such as DNA and HSA.
Transition Metal Nitrosyls: Statistics, Charge Estimates via CDVR, and Studies of Tetradentate Chelate Diamides (pddi)M and (pddi)MNO (M = Cr, Fe, and Co)
2023, Organometallics
Correlations of ν(NO) with d(NO), /MNO, and charge from roughly 560 first row transition metal complexes are graphically depicted. An equation of charge (c _NO = {ν(NO) – 1960}/450 cm^–1) was phenomenologically derived within the parameters set by CDVR (charge distribution via reporters) and used to show that nitrosyl should realistically not be interpreted as bound “NO⁺”. The tetradentate chelate [Me₂C{CHN(1,2-C₆H₄)NH(2,6-iPr₂C₆H₃)₂}]n ((pddi)n) was shown to produce (pddi)M (2-M; M = Cr, Fe, Co) as precursors to mononitrosyls, (pddi)MNO (2-MNO). Significant electronic complexity was observed in 2-M and 2-MNO (M = Cr and Fe), and 2-Co was unstable, degrading to {[κ³-N,N,N-1,2-ArNC₆H₄NCHCMe₂NO]Co}₂ (3; Ar = 2,6-iPr₂C₆H₃). Structural features of 3 conform to formally S = 1/2 Co(II) centers antiferromagnetically coupled to alkylnitroso radical anions, that is, LS [(LX^–) Co^2+(↑)RNO^(−↓)][(LX^–)Co^2 + (↓)RNO^(−↑)], whose charge elements are consistent with the tenets of CDVR.
Ferrous nitrosylated cytochrome c: The unusual strength of the proximal His18-Fe bond
2023, Journal of Inorganic Biochemistry
NO binding to horse heart cytochrome c (hhcyt c) has been investigated as a function of pH by both optical absorption and EPR spectroscopies. Lowering pH from 3.5 to 1.5 induces: (i) a blue-shift of the maximum of the optical absorption spectrum in the Soret region from 415 to about 404 nm, and (ii) the appearance of a strong three hyperfine splitting in the g_z region of the EPR spectrum. Both spectroscopic features indicate the cleavage of the proximal His18-Fe(II)-NO bond giving rise to the five-coordinated Fe(II)-NO species. By quantification of the relative weight for the six- and the five-coordinated component in the EPR spectra, the pK_a value was determined. The apparent pK_a of the proximal His Nε atom (1.8 ± 0.1) is unusually low for a ferrous nitrosylated form since in all investigated ferrous NO-bound heme-proteins the pK_a value for the cleavage of the proximal His-Fe(II) bond ranges between 3.7 and 5.8. The pK_a value of ferrous nitrosylated hhcyt c indicates that the strength of the proximal His18-Fe(II) bond (= 27.9 kJ/mol) is about 10–22 kJ/mol higher than that observed in all investigated heme-proteins. The strong coordination of the heme-Fe atom by His18 is extremely important to maintain the redox efficiency of cyt c and to keep apoptosis under control. This is a crucial point in tissues, such as retina, where apoptosis might trigger macular degenerative processes.
Bent-Linear Isomerism and a Caveat on Bond Angle Distortion Anomalies in CpMo(NO)(η<sup>3</sup>-Methallyl)NCO
2023, Journal of Organometallic Chemistry
The displacement of the iodide ligand in (+)-(Cp)Mo(NO)(η³-methallyl)I, (+)-1, by treatment with silver(I) isocyanate yields (+)-(Cp)Mo(NO)(η³-methallyl)(NCO), (+)-2, with retention of configuration at the metal and was found to have the S_Mo configuration by X-ray crystallography. The X-ray data also showed the presence of two structure types in the unit cell of (+)-2, one bent and one linear with ∠MoNC bond angles of 154.4(4)° and 173.4(4)° respectively. In contrast, crystals of rac-2 show only one structure in the solid with an intermediate angle of 165.7(4). If (+)-2 is prepared via conversion of (+)-1 first to the carbonyl, by abstraction of iodide and treatment with CO, and subsequently sodium azide, yielded crystals of (+)-2 which showed varying angles ∠MoNC that appeared to be distortion isomers. Closer inspection of these products revealed an admixture of the intermediate azide compound, (+)-(Cp)Mo(NO)(η³-methallyl)N_3, (+)-3, in the sample that was predominantly (+)-2. Mixtures of (+)-3 and (+)-2 or (-)-3 and (-)-2-co-crystallize and the results of X-ray structures of such mixtures appear to show 2 with varying bond angles ∠MoNC depending on the percentage of 3 in them. For example crystals with 85% of (-)-2 show ∠MoNC bond angles of 148.9(5)° and 171.9(5)°. This compares with the ∠MoNN in pure azide (+)-3 of 123.7(6)°
Bacterial nitric oxide reductase (NorBC) models employing click chemistry
2023, Journal of Inorganic Biochemistry
Bacterial NO Reductase (NorBC or cNOR) is a membrane-bound enzyme found in denitrifying bacteria that catalyzes the two-electron reduction of NO to N₂O and water. The mechanism by which NorBC operates is highly debated, due to the fact that this enzyme is difficult to work with, and no intermediates of the NO reduction reaction could have been identified so far. The unique active site of NorBC consists of a heme b₃/non-heme Fe_B diiron center. Synthetic model complexes provide the opportunity to obtain insight into possible mechanistic alternatives for this enzyme. In this paper, we present three new synthetic model systems for NorBC, consisting of a tetraphenylporphyrin-derivative clicked to modified BMPA-based ligands (BMPA = bis(methylpyridyl)amine) that model the non-heme site in the enzyme. These complexes have been characterized by EPR, IR and UV–Vis spectroscopy. The reactivity with NO was then investigated, and it was found that the complex with the BMPA-carboxylate ligand as the non-heme component has a very low affinity for NO at the non-heme iron site. If the carboxylate functional group is replaced with a phenolate or pyridine group, reactivity is restored and formation of a diiron dinitrosyl complex was observed. Upon one-electron reduction of the nitrosylated complexes, following the semireduced pathway for NO reduction, formation of dinitrosyl iron complexes (DNICs) was observed in all three cases, but no N₂O could be detected.

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Principles of structure, bonding, and reactivity for metal nitrosyl complexes

First page preview

J. Inorg. Nucl. Chem.

J. Inorg. Nucl. Chem.

Coord. Chem. Rev.

Inorg. Chim. Acta

Inorg. Chim. Acta

Spectrochim. Acta

J. Mol. Struct.

Inorg. Chim. Acta

J. Organometal. Chem.

Inorg. Chim. Acta

Proc. Roy. Soc., London

J. Chem. Educ.

J. Chem. Educ.

Quart. Rev. Chem. Soc.

Prog. Inorg. Chem.

Advan. Organometal. Chem.

Inorg. Chim. Acta Rev.

M.T.P. Int. Rev. Sci., Inorg. Chem., Ser. One

M.T.P Int. Rev. Sci., Phys. Chem., Ser. One

Inorg. Chim. Acta Rev.

J. Chem. Soc.

Inorg. Chem.

J. Amer. Chem. Soc.

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

Acta Chem. Scand.

Inorg. Chem.

Proc. Chem. Soc., London

J. Chem. Soc.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Soc. A

Chem. Commun.

J. Chem. Phys.

Chem. Commun.

Inorg. Chem.

Angew. Chem. Internat. Edit.

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Proc. Nat. Acad. Sci. USA

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