To exploit the magnetic interactions of multiple metals, heterometallic one-dimensional (1D) chain containing three kinds of metals, Rh, Pt, and Mn, where [Rh2(O2CCH3)4] and [Pt2Mn(piam)4(NH3)4]2+ (piam = pivalamidate) are connected...

For mechanism of decarboxylation reaction, all textbooks show that the electron moves from the pi_C=O bond. However, the most donating bond orbital in the carbonyl group should be the lone pair(s) on the oxygen. Thus, a picture of orbital theory with delocalization from a lone pair should be more appropriate than that from the pi_C=O orbital. We confirmed our idea by theoretical calculation. In the TS, if we use 2-substituted b-ketoacids, the boat-form conformation should result in exclusively preferred generation of <i>E</i>-enolates. Normally, decarboxylation reaction performs in polar solvent, so that the resulting enols should be transformed to the corresponding ketones by tautomerization. Suppose we use the heteroatoms to obtain the enolate or enol ethers without tautomerization, it would offer a diastereoselective enol(ate) synthesis with regioselectivity, since the C=C double bond should always be introduced between two carbonyl groups. After screening the heteroatoms by the theoretical calculations, we found that boron is suitable for this purpose. We confirmed our idea by theoretical calculations, offering a new boradecarboxylation reaction to produce enolates diastereoselecitively and regioselectively.

For the mechanism of decarboxylation reactions, all textbooks show electrons moving from the πC=O bond. However, the most electron-donating bond orbital in the carbonyl group is expected to be the lone pair(s) on the oxygen. Thus, orbital theory with delocalization from a lone pair may be more appropriate than delocalization from the πC=O orbital. We confirmed our idea by theoretical calculations. In the TS, if we use 2-substituted

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Paramagnetic trinuclear complexes, trans-[Pt 2 M-(piam) 4 (NH 3 ) 4 ](ClO 4 ) x (t-M; piam = pivalamidate, M = Mn, Fe, Co, Ni, and Cu, x = 2 or 3), aligned as Pt−M−Pt were successfully synthesized and characterized. The dihedral angles between the Pt and M coordination planes in t-M are approximately parallel, showing straight metal−metal bonds with distances of approximately 2.6 Å. Except for t-Fe, the trinuclear complexes are dimerized with close contact (approximately 3.9 Å) between the end Pt atoms to form Pt−M−Pt•••Pt−M−Pt alignments with high-spin M(+2) containing five (t-Mn), three (t-Co), two (t-Ni), and one (t-Cu) unpaired electrons localized on M atoms. Several physical measurements and calculations revealed that the dimerized structures were maintained in MeCN, where cyclic voltammograms for t-M exhibited two-step oxidation and reduction attributed to Pt−Mvia mixed-valent states. Magnetic susceptibility measurements for t-M showed antiferromagnetic interaction, t-Mn: J = −0.9 cm −1 , t-Co: J = −3.5 cm −1 , t-Ni: J = −7.3 cm −1 , and t-Cu: J = 0.0 cm −1 , between the two M centers with distances of 9.0 Å through Pt•••Pt bonds.