Divergent reactivity of nitric oxide with metal–metal quintuple bonds

Wu, Pei‐Fang; Liu, Shih-Cheng; Shieh, Yun-Jen; Kuo, Ting‐Shen; Lee, Gene‐Hsiang; Wang, Yu; Tsai, Yi‐Chou

doi:10.1039/c3cc37118b

Cited by 34 publications

(21 citation statements)

References 41 publications

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“…In this study, we have not concerned ourselves with six-coordinate {M(NO) 2 } 6 (M = V, 38 Cr, 39,40 was analyzed in an earlier DFT study and is thought to reflect stereoelectronic constraints imposed by the porphyrin ligand. 43 Also excluded from this study are six-coordinate transdinitrosyl species, examples of which are provided by {M(NO) 2 } 8 derivatives of porphyrin-and phthalocyanine-type ligands.…”

Section: Resultsmentioning

confidence: 99%

Stereochemistry of Transition-Metal Dinitrosyl Complexes. A Molecular Orbital Rationale for the Attracto and Repulso Conformations

Ghosh

Conradie

2019

Inorg. Chem.

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Transition metal dinitrosyl complexes constitute a fairly large class of compounds, exemplified by some 500 structures in the Cambridge Structural Database. While many of the complexes exhibit a claw-like cis-attracto conformation, a handful of them exhibit a peculiar repulso conformation, in which the two NO groups are splayed outward and away from each other. Surprisingly, no computational study to date has attempted to explain the existence of these two limiting conformations of cis-dinitrosyl complexes. Careful examination of the large body of structural data and DFT-based molecular orbital analyses have identified both specific Enemark-Feltham electron counts and metal-ligand orbital interactions as crucial to each of the two conformations. Thus, the common attracto conformation, which is favored by as many as four metal(d)-NO(π*) orbital interactions, is observed most characteristically in four-and fivecoordinate cis-{M(NO) 2 } 8 complexes. The rarer repulso conformation, characterized by an unusually wide NMN´ angle, appears to be typical of pseudotetrahedral {M(NO) 2 } 10 complexes involving 4d and 5d transition metals. These complexes exhibit an a 1-symmetry (under a C 2v molecular point group) metal(d)-NO(π*) orbital interaction that uniquely favors a repulso geometry. This orbital interaction, however, appears to be weaker for 3d orbitals, which are significantly smaller than 4d and 5d orbitals. Pseudotetrahedral {M(NO) 2 } 10 complexes involving a 3d transition metal accordingly thus tend to exhibit an attracto conformation for hard, nitrogenbased supporting ligands but repulso-like/borderline conformations for soft phosphine and thioether-type supporting ligands.

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Section: Resultsmentioning

confidence: 99%

Stereochemistry of Transition-Metal Dinitrosyl Complexes. A Molecular Orbital Rationale for the Attracto and Repulso Conformations

Ghosh

Conradie

2019

Inorg. Chem.

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“…Aer 24 hours cells were replenished with fresh media and the test samples were added to the cells. Different concentrations (10,20,40, & 80 mg L À1 ) of [dha-aapH] Schiff base and its [Mo(NO) 2 (dha-aap)OH] complex were added to wells in triplicates. Cells were incubated with the solution compounds for 24 hours at 37 C in 5% CO 2 .…”

Section: Biological Assaysmentioning

confidence: 99%

“…The use of various functionals and basis sets with respect to nitrosyl complexes to go through the chemical nature of NO as neutral or charged species has gained much importance in this regard. [38][39][40][41][42][43] The selection of ligand for complexation is an important and careful job for synthesizing a complex. Pyrazolone based Schiff base as ONO donor ligand is the second co-ligand aer NO targeted in this study.…”

Section: Introductionmentioning

confidence: 99%

Nitric oxide functionalized molybdenum(0) pyrazolone Schiff base complexes: thermal and biochemical study

Mir

Maurya

2018

RSC Adv.

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“…However, the employment of the more sterically congested terphenyl ligand 2,6‐(2,4,6‐ i Pr 3 C 6 H 2 ) 2 C 6 H 3 effectively prevented two Cr atoms from coupling to each other . On the other hand, all the N‐donor‐supported Cr−Cr quintuple bonds were even shorter but more reactive; they were readily cleaved upon reacting with small inorganic molecules and organic functionalities,,, in contrast with the quintuply bonded molybdenum amidinate dimers…”

Section: Figurementioning

confidence: 99%

Reversible Cleavage/Formation of the Chromium–Chromium Quintuple Bond in the Highly Regioselective Alkyne Cyclotrimerization

Huang

Liu

et al. 2017

Angew Chem Int Ed

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Herein we report the employment of the quintuply bonded dichromium amidinates [Cr{κ -HC(N-2,6- Pr C H )(N-2,6-R C H )}] (R=iPr (1), Me (7)) as catalysts to mediate the [2+2+2] cyclotrimerization of terminal alkynes giving 1,3,5-trisubstituted benzenes. During the catalysis, the ultrashort Cr-Cr quintuple bond underwent reversible cleavage/formation, corroborated by the characterization of two inverted arene sandwich dichromium complexes (μ-η :η -1,3,5-(Me Si) C H )[Cr{κ -HC(N-2,6- Pr C H )(N-2,6-R C H )}] (R= Pr (5), Me (8)). In the presence of σ donors, such as THF and 2,4,6-Me C H CN, the bridging arene 1,3,5-(Me Si) C H in 5 and 8 was extruded and 1 and 7 were regenerated. Theoretical calculations were employed to disclose the reaction pathways of these highly regioselective [2+2+2] cylcotrimerization reactions of terminal alkynes.

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Divergent reactivity of nitric oxide with metal–metal quintuple bonds

Abstract: Reactions of NO with the quintuple bonded chromium and molybdenum amidinate dimers, respectively, gave dichromium nitrosyl nitrito amidinato complexes, and the quadruple bonded dimolybdenum nitrito amidinato species with a paddlewheel configuration.

Cited by 34 publications

References 41 publications

Stereochemistry of Transition-Metal Dinitrosyl Complexes. A Molecular Orbital Rationale for the Attracto and Repulso Conformations

Stereochemistry of Transition-Metal Dinitrosyl Complexes. A Molecular Orbital Rationale for the Attracto and Repulso Conformations

Nitric oxide functionalized molybdenum(0) pyrazolone Schiff base complexes: thermal and biochemical study

Reversible Cleavage/Formation of the Chromium–Chromium Quintuple Bond in the Highly Regioselective Alkyne Cyclotrimerization

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