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Synthesis, Structure, and Reactivity of Magnesium Pentalenides.

ABSTRACT: The first magnesium pentalenide complexes have been synthesized via deprotonative metalation of 1,3,4,6-tetraphenyldihydropentalene (Ph₄PnH₂) with magnesium alkyls. Both the nature of the metalating agent and the reaction solvent influenced the structure of the resulting complexes, and an equilibrium between Mg[Ph₄Pn] and [ⁿBuMg]₂[Ph₄Pn] was found to exist and investigated by NMR, XRD, and UV-vis spectroscopic techniques. Studies on the reactivity of Mg[Ph₄Pn] with water, methyl iodide, and trimethylsilylchloride revealed that the [Ph₄Pn]^2- unit undergoes electrophilic addition at 1,5-positions instead of 1,4-positions known for the unsubstituted pentalenide, Pn^2-, highlighting the electronic influence of the four aryl substituents on the pentalenide core. The ratio of syn/anti addition was found to be dependent on the size of the incoming electrophile, with methylation yielding a 60:40 mixture, while silylation yielded exclusively the anti-isomer.

SUBMITTER: Sanderson HJ

PROVIDER: S-EPMC10548416 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature

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Synthesis, Structure, and Reactivity of Magnesium Pentalenides.

Sanderson Hugh J HJ Kociok-Köhn Gabriele G Hintermair Ulrich U

Inorganic chemistry 20230915 39

The first magnesium pentalenide complexes have been synthesized via deprotonative metalation of 1,3,4,6-tetraphenyldihydropentalene (Ph4PnH2) with magnesium alkyls. Both the nature of the metalating agent and the reaction solvent influenced the structure of the resulting complexes, and an equilibrium between Mg[Ph4Pn] and [nBuMg]2[Ph4 ...[more]

PMID: 37712911

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Project description:Four heterotrinuclear complexes containing the ligands 3,5-bis(2-pyridyl)pyrazolate (bpp-) and 2,2':6',2''-terpyridine (trpy) of the general formula {[RuII(trpy)]2(μ-[M(X)2(bpp)2])}(PF6)2, where M = CoII, MnII and X = Cl-, AcO- (M = CoII, X = Cl-: Ru2Co-Cl2 ; M = MnII, X = Cl-: Ru2Mn-Cl2 ; M = CoII, X = AcO-: Ru2Co-OAc2 ; M = MnII, X = AcO-: Ru2Mn-OAc2 ), have been prepared for the first time. The complexes have been characterized using different spectroscopic techniques such as UV-vis, IR, and mass spectrometry. X-Ray diffraction analyses have been used to characterize the Ru2Mn-Cl2 and Ru2Mn-OAc2 complexes. The cyclic voltammograms (CV) for all four complexes in organic solvent (CH3CN or CH2Cl2) display three successive reversible oxidative waves corresponding to one-electron oxidations of each of the three metal centers. The oxidized forms of the complexes Ru2Co-OAc2 and Ru2Mn-OAc2 are further characterized by EPR and UV-vis spectroscopy. The magnetic susceptibility measurements of all complexes in the temperature range of 2-300 K reveal paramagnetic properties due to the presence of high spin Co(ii) and Mn(ii) centers. The complexes Ru2Co-OAc2 and Ru2Mn-OAc2 act as precatalysts for the water oxidation reaction, since the acetato groups are easily replaced by water at pH = 7 generating the active catalysts, {[Ru(H2O)(trpy)]2(μ-[M(H2O)2(bpp)2])}4+ (M = CoII: Ru2Co-(H2O)4 ; M = MnII: Ru2Mn-(H2O)4 ). The photochemical water oxidation reaction is studied using [Ru(bpy)3]2+ as the photosensitizer and Na2S2O8 as a sacrificial electron acceptor at pH = 7. The Co containing complex generates a TON of 50 in about 10 minutes (TOFi = 0.21 s-1), whereas the Mn containing complex only generates a TON of 8. The water oxidation reaction of Ru2Co-(H2O)4 is further investigated using oxone as a sacrificial chemical oxidant at pH = 7. Labelled water oxidation experiments suggest that a nucleophilic attack mechanism is occurring at the Co site of the trinuclear complex with cooperative involvement of the two Ru sites, via electronic coupling through the bpp- bridging ligand and via neighboring hydrogen bonding.

Dataset Information

Synthesis, Structure, and Reactivity of Magnesium Pentalenides.

Publications

Synthesis, Structure, and Reactivity of Magnesium Pentalenides.

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