Evaluating the Catalytic Activities of PNCNP Pincer Group 10 Metal Hydride Complexes: Pd-Catalyzed Reduction of CO2 to the Formic Acid Level with NH3·BH3 and NaBH4 under Ambient Conditions.

In order to develop efficient protocols for CO2 reduction with less expensive and more convenient hydrogen sources, the catalytic reactivities of group 10 metal hydride complexes supported by a PNCNP pincer ligand, [2,6-(tBu2PNH)2C6H3]MH (M = Ni, 1a; Pd, 1b; Pt, 1c), against the hydroboration of CO2 with NH3·BH3 and NaBH4 have been explored. Both 1a and 1b readily react with CO2 at room temperature to form the corresponding formato complexes, [2,6-(tBu2PNH)2C6H3]MOC(O)H (M = Ni, 2a; Pd, 2b), in nearly quantitative yields. Treatment of NH3·BH3 with CO2 (1 atm) in 1,4-dioxane or THF at room temperature in the presence of 0.05-1.0 mol % of 1b followed by hydrolysis of the resulting mixtures produces formic acid in 105-186% yields, and initial turnover frequencies of up to 2000 h-1 are observed. In the presence of 1.0 mol % of 1b, NaBH4 reacts with CO2 (1 atm) in THF at room temperature to form NaB[OC(O)H]4 (3) in 87% isolated yield. In situ NMR spectroscopy indicates that the reactions proceed through the insertion of the C═O bond in CO2 into the Pd-H bond in 1b to form 2b, which sequentially reacts with the hydrides in NH3·BH3 or NaBH4 to produce boron formato species and regenerate 1b. This work represents one of the rare examples of catalytic transfer hydrogenation of CO2 with NH3·BH3 to the formic acid level under very mild conditions without any additives and also the first example of 4 equiv of CO2 uptake by NaBH4 in a reaction.

Noncatalyzed Reduction of Nitriles to Primary Amines with Ammonia Borane.

The preparation of primary amines from nitriles has been a subject of continuing interest, and many different methods have been reported for this process. We report in this paper an alternative method for transforming nitriles into primary amines. In this work, a wide range of nitriles were reduced to primary amines by 1.2 equiv of ammonia borane under thermal decomposition conditions without any catalyst and the corresponding primary amines were isolated in good to excellent yields. The reactions are environmentally benign with H2 and NH3 generated as byproducts. The reactions are also tolerant of many functional groups. Nitriles are likely reduced by the in situ-generated aminodiborane, the application of which in organic synthesis has never been reported before. By using our protocol, primary amines containing multifluorinated aromatic rings, which are greatly important in pharmaceutical synthesis and have rarely been prepared via catalytic processes, were successfully prepared.

Structures of nickel chloride and thiolate complexes supported by PCN and POCOP pincer ligands and catalytic reactivity of the chloride complexes.

Nickel chloride and thiolate complexes supported by benzene-pyridine-based nonsymmetrical PCN pincer ligands, [2-(tBu2PO)-6-(2-pyrindinyl-4-R)-C6H3]NiX (R = H, CH3, CF3; X = Cl, SH, SPh), were synthesized and fully characterized. The structures of these complexes and the catalytic reactivity of the chloride complexes were investigated along with the related POCOP counterparts [2,6-(tBu2PO)2C6H3]NiX (X = Cl, SH). It was found that the composition and substitution of the pincer backbone evidently influence the structures and catalytic reactivity. The Ni-P and Ni-Cipso bond lengths in the PCN complexes are significantly shorter than those in the POCOP complex. The Ni-Cl and Ni-S bond lengths in the PCN complexes are longer than those in the POCOP complexes. An electron rich pyrindinyl ring in the PCN complexes makes the Ni-Cl bond longer. The Ni-N bond length is more sensitive to the auxiliary ligand compared with the Ni-P bond length in the PCN complexes. The PCN chloride complexes were found to be active catalysts for selective hydration of nitriles to primary amides in the presence of NaOH at 80 °C and the catalytic activity increases with the increase of electron richness of the pyridinyl ring. However, the corresponding POCOP counterpart is inactive under the same conditions.

Reactions and catalytic applications of a PNCNP pincer palladium hydride complex.

A palladium(II) hydride complex supported by a benzene-based PNCNP pincer ligand, [2,6-(tBu2PNH)2C6H3]PdH (1), has been synthesized via two different routes: the reaction of the corresponding chloride complex with LiAlH4 and the reaction of the corresponding nitrate complex with KOCH3. Complex 1 exhibits strong deprotonating ability and versatile catalytic activity. Acetamide can be readily deprotonated by complex 1 to form the corresponding acetamido complex, [2,6-(tBu2PNH)2C6H3]PdNHC(O)CH3, in high yield. Complex 1 is an active catalyst for both the dehydrogenation of methanol to formaldehyde under mild conditions and direct hydration of nitriles to primary amides. Particularly, the direct hydration of nitriles to primary amides catalysed by complex 1 represents the most efficient palladium catalytic system for this type of reaction. A wide range of nitriles have been successfully hydrated to primary amides with 100% selectivity and good to excellent isolated yields. The possible reaction mechanisms are discussed.