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Reversible carbon-boron bond formation at platinum centers through σ-BH complexes.

ABSTRACT: A reversible carbon-boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(ii) complex [Pt(I ^t BuⁱPr')(I ^t BuⁱPr)][BAr^F], 1, with tricoordinated boranes HBR₂. X-ray diffraction studies provided structural snapshots of the sequence of reactions involved in the process. At low temperature, we observed the initial formation of the unprecedented σ-BH complexes [Pt(HBR₂)(I ^t BuⁱPr')(I ^t BuⁱPr)][BAr^F], one of which has been isolated. From -15 to +10 °C, the σ-BH species undergo a carbon-boron coupling process leading to the platinum hydride derivative [Pt(H)(I ^t BuⁱPr-BR₂)(I ^t BuⁱPr)][BAr^F], 4. Surprisingly, these compounds are thermally unstable undergoing carbon-boron bond cleavage at room temperature that results in the 14-electron Pt(ii) boryl species [Pt(BR₂)(I ^t BuⁱPr)₂][BAr^F], 2. This unusual reaction process has been corroborated by computational methods, which indicate that the carbon-boron coupling products 4 are formed under kinetic control whereas the platinum boryl species 2, arising from competitive C-H bond coupling, are thermodynamically more stable. These findings provide valuable information about the factors governing productive carbon-boron coupling reactions at transition metal centers.

SUBMITTER: Rios P

PROVIDER: S-EPMC8179255 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The oxidation of the tribenzylphosphine derivative of the doubly cylcometallated platinum(ii) complex of diphenylpyridine, 1, with PhICl2 led, as a first step, to the formation of a highly electrophilic metal centre which attacked the benzyl phosphine to give a triply cyclometallated species as the arenium ion. The highly acidic arenium ion protonated unreacted starting 1, a reaction that could be supressed by the addition of water, and gave the neutral species 2(t). Octahedral complex 2(t) was induced to reductively couple, with two five-membered rings coupling to give square planar complex 5 containing a nine-membered ring. The crystal structure of 5 showed the nine-membered ring to span trans across the square planar metal accompanied by considerable distortion: the P-Pt-N bond angle is 155.48(5)°. Oxidation of 5 with PhICl2 resulted in the addition of two chlorides and a change of the nine-membered ring ligand coordination to cis at an octahedral centre, still with considerable distortions: the P-Pt-N bond angle in the crystal structure of 6 is 99.46(5)°. Treatment of 2(t) with AgBF4 also induced a coupling to give a nine-membered ring, and the fluxional three coordinate complex 7. A mono-methylated version of 1, Me-1, was prepared and similar reactions were observed. The presence of the methyl group allowed us to observe selectivity in the coupling reaction to give the nine-membered ring, with two products (a-Me-7 and b-Me7) being initially formed in the ratio 7?:?1. The concentrations of two products changed with time giving a final ratio of 1?:?8 at room temperature (half-life 48 hours), the equilibration being made possible by a reversible C-C bond forming reaction. Reaction of complexes 7 with CO or hydrogen left the nine-membered ring intact, though oxidative degradation resulted in decomplexation of the phosphine donor, accompanied by formation of a P 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O group.

Project description:The 4-diazabicyclo[2. 2. 2] octane, DABCO, had widely established with gigantic and celestial applications on catalysis for carbon-carbon bond formation reactions. Thus, it has been employed to synthesize the alkyl 2-(hydroxyl (nitrophenyl) methyl)acrylate by the reaction of arylaldehydes and alkylacrylates under a mild condition with good yields. First of all, reaction was examined effect of various solvents, such as water, MeOH, Dioxane, DMSO, t-Butanol, DMF, Toluene, and THF and THF was the best solvent in term of yield. Next, the room temperature (R.T) was the optimized condition than 60 °C and 80 °C. The overall reaction progress was monitored in presence of DABCO, Et3N, C2H5ONa, C4H9OK, (CH3)3COK and pyridine catalysts with THF solvents at room temperatures, and calculated the amount for superior of catalyst. There was no product obtained in presence of catalysts, such as Et3N, C2H5ONa, C4H9OK, (CH3)3COK and pyridine. But in present of DABCO, this reaction has proceeded and monitored the concentration of catalyst and various temperature effects on reaction progress. In addition, the computational approaches for speculative investigation of solvents effect has employed for predicating and comparatively verified with the proposed reaction mechanism in presence of DABCO catalyst through the Density Functional Theory (DFT). The most acceptable tools for the thermodynamic had been illustrated to get the reaction kinetics by formation energy, entropy, enthalpy for reactant, product and transition state. Finally, the Gibbs free energy for reactions from the reactants and product has calculated to predict the occurring spontaneously possibility with and without solvents, and it is said that the reaction is spontaneously occurred through the water, DMSO, THF solvent although it is opposed fact without solvent even other solvents. It might be concluded that the optimization conditions of reaction are the THF solvent in presence of 20% DABCO catalyst at room temperature with high (about 90%) throughout 6-8 h where the 4- position of nitro group in arylaldehyde is the most preferable in case of time and yield.

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Reversible carbon-boron bond formation at platinum centers through σ-BH complexes.

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