A facile synthesis of heavy alkali metal octahydrotriborates (MB3H8; M=K, Rb, and Cs) has been developed. It is simply based on reactions of the pure alkali metals with THF⋅BH3, does not require the use of electron carriers or the addition of other reaction media such as mercury, silica gel, or inert salts as for previous procedures, and delivers the desired products at room temperature in very high yields. However, no reactions were observed when pure Li or Na was used. The reaction mechanisms for the heavy alkali metals were investigated both experimentally and computationally. The low sublimation energies of K, Rb, and Cs were found to be key for initiation of the reactions. The syntheses can be carried out at room temperature because all of the elementary reaction steps have low energy barriers, whereas reactions of LiBH4/NaBH4 with THF⋅BH3 have to be carried out under reflux. The high stability and solubility of KB3H8 were examined, and a crystal structure thereof was obtained for the first time.

The reduction of CO2 is of great importance. In this paper, different types of bis(phosphinite) (POCOP) pincer nickel complexes, [2,6-(R2PO)2C6H3]NiX (R = tBu, iPr, Ph; X = SH, N3, NCS), were applied to the catalytic hydroboration of CO2 with catecholborane (HBcat). It was found that pincer complexes with tBu2P or iPr2P phosphine arms are active catalysts for this reaction in which CO2 was successfully reduced to a methanol derivative (CH3OBcat) with a maximum turnover frequency of 1908 h−1 at room temperature under an atmospheric pressure of CO2. However, complexes with phenyl-substituted phosphine arms failed to catalyze this reaction—the catalysts decomposed under the catalytic conditions. Complexes with iPr2P phosphine arms are more active catalysts compared with the corresponding complexes with tBu2P phosphine arms. For complexes with the same phosphine arms, the catalytic activity follows the series of mercapto complex (X = SH) ≈ azido complex (X = N3) >> isothiocyanato complex (X = NCS). It is believed that all of these catalytic active complexes are catalyst precursors which generate the nickel hydride complex [2,6-(R2PO)2C6H3]NiH in situ, and the nickel hydride complex is the active species to catalyze this reaction.

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Intramolecular nucleophilic attack on the metal or the phosphorus center of a POCOP pincer metal complex is lethal to the robust pincer backbone.