A reactive coordinatively saturated Mo(<scp>iii</scp>) complex: exploiting the hemi-lability of tris(<i>tert</i>-butoxy)silanolate ligands

Pucino, Margherita; Allouche, Florian; Gordon, Christopher P.; Wörle, Michael; Mougel, Victor; Copéret, Christophe

doi:10.1039/c9sc01955c

Cited by 29 publications

(36 citation statements)

References 54 publications

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“…[29,30] Interestingly, the alkyne CÀ C and MÀ C bonds display the same length in both 1a and 1b proving that C 2 Me 2 is naturally a better donor than HC 2 Ph and C 2 Ph 2 . Compared to a recently published five-coordinate Mo(III) C 2 Me 2 adduct with an alkyne CÀ C distance of 1.283 Å, [55] the CÀ C distance in Mo(II) (1b) is slightly longer, while that in Mo(IV) (6b) is a little shorter displaying a nice trend when comparing the different oxidation states of the Mo center.…”

Section: Synthesis Of Oxido Complexescontrasting

confidence: 65%

Synthesis and Reactivity of Molybdenum and Tungsten Alkyne Complexes Containing 6‐Methylpyridine‐2‐thiolate Ligands

Ehweiner

Ćorović

Belaj

et al. 2021

Helvetica Chimica Acta

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A series of M(II) and M(IV) (M = Mo, W) alkyne adducts employing two 6-methylpyridine-2-thiolate (6-MePyS) ligands was synthesized and investigated towards the nucleophilic attack of PMe 3 on the coordinated alkynes. For this approach, 2-butyne (C 2 Me 2 ), phenylacetylene (HC 2 Ph), and diphenylacetylene (C 2 Ph 2 ) were used. For the exploration of an intramolecular attack, but-3-yn-1-ol (HCCCH 2 CH 2 OH) was coordinated to the metal centers. A nucleophilic attack of PMe 3 was observed in [W(CO)(HC 2 Ph)(6-MePyS) 2 ] yielding an η 2 -vinyl compound. Reaction of [W(CO)(C 2 Ph 2 )(6-MePyS) 2 ] with excess PMe 3 resulted in the selective coordination of one molecule of PMe 3 concomitant with decoordination of the nitrogen atom of one 6-MePyS ligand. In contrast, the W(IV) complexes did not react with PMe 3 . While no selectivity was observed in the reaction of the Mo(II) compounds with PMe 3 , alkynes in the Mo(IV) compounds were replaced by PMe 3 . Addition of Et 3 N to the but-3-yn-1-ol complexes did not lead to the anticipated formation of 2,3-dihydrofuran.

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Section: Synthesis Of Oxido Complexescontrasting

confidence: 65%

Synthesis and Reactivity of Molybdenum and Tungsten Alkyne Complexes Containing 6‐Methylpyridine‐2‐thiolate Ligands

Ehweiner

Ćorović

Belaj

et al. 2021

Helvetica Chimica Acta

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“…In addition, the MoL 3 fragment is isolobal to a nitrogen atom by its three unpaired electrons populating the mainly d

_{normalz^{2}}

, d xz and d yz molecular orbitals, providing a significant thermodynamic stability to the corresponding Mo nitrides. A second Mo III complex displaying similar reactivity towards dinitrogen was reported more than 20 years later [30] . When the octahedral complex [Mo III (OSi(O t Bu) 3 ) 3 ] ( 3 ) was exposed to dinitrogen, the corresponding mononuclear nitride complex ( 4 ) could be formed (Scheme 5 b).…”

Section: Dissociative Mechanismmentioning

confidence: 55%

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Masero

Perrin

Dey

et al. 2020

Chemistry A European J

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Dinitrogen (N2) is the most abundant gas in Earth's atmosphere, but its inertness hinders its use as a nitrogen source in the biosphere and in industry. Efficient catalysts are hence required to ov. ercome the high kinetic barriers associated to N2 transformation. In that respect, molecular complexes have demonstrated strong potential to mediate N2 functionalization reactions under mild conditions while providing a straightforward understanding of the reaction mechanisms. This Review emphasizes the strategies for N2 reduction and functionalization using molecular transition metal and actinide complexes according to their proposed reaction mechanisms, distinguishing complexes inducing cleavage of the N≡N bond before (dissociative mechanism) or concomitantly with functionalization (associative mechanism). We present here the main examples of stoichiometric and catalytic N2 functionalization reactions following these strategies.

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“…27,28 After this milestone work, other research groups reported the formation of similar nitride complexes via direct cleavage of the bridging dinitrogen on dinitrogen-bridged dinuclear complexes. [29][30][31][32][33][34][35][36][37][38][39][40][41][42] Interestingly, Cummins and co-workers reported the formation of nitriles from reactions of nitride complexes with acid chlorides. [43][44][45] This research group successfully achieved a pseudo catalytic cycle to convert dinitrogen into nitriles with a stoichiometric amount of transition metal complexes.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of molybdenum–nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles

et al. 2022

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A reactive coordinatively saturated Mo(iii) complex: exploiting the hemi-lability of tris(tert-butoxy)silanolate ligands

Abstract: Hemilabile tris(tert-butoxy)silanolate ligands allow stabilizing a mononuclear octahedral Mo(iii) complex without quenching its reactivity towards small molecules (N2, CO2, N2O).

Cited by 29 publications

References 54 publications

Synthesis and Reactivity of Molybdenum and Tungsten Alkyne Complexes Containing 6‐Methylpyridine‐2‐thiolate Ligands

Synthesis and Reactivity of Molybdenum and Tungsten Alkyne Complexes Containing 6‐Methylpyridine‐2‐thiolate Ligands

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Reactivity of molybdenum–nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles

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