A method is presented to design magnetic molecules in which the exchange interaction between adjacent metal ions is controlled by electron density withdrawal through their bridging ligands. We synthesized a novel Mn(4) cluster in which the choice of the bridging carboxylate ligands (acetate, benzoate, or trifluoroacetate) determines the type and strength of the three magnetic exchange couplings (J(1), J(2), and J(3)) present between the metal ions. Experimentally measured magnetic moments in high magnetic fields show that, upon electron density withdrawal, the main antiferromagnetic exchange constant J(1) decreases from -2.2 K for the [Mn(4)(OAc)(4)] cluster to -1.9 K for the [Mn(4)(H(5)C(6)COO)(4)] cluster and -0.6 K for the [Mn(4)(F(3)CCOO)(4)] cluster, while J(2) decreases from -1.1 K to nearly 0 K and J(3) changes to a small ferromagnetic coupling. These experimental results are further supported with density-functional theory calculations based on the obtained crystallographic structures of the [Mn(4)(OAc)(4)] and [Mn(4)(F(3)CCOO)(4)] clusters.

A variety of allylic O,O‐ and N,O‐acetals were synthesized using a mild palladium‐catalyzed coupling of an alcohol or sulfonamide with an alkyl or aryl 1,2‐propadienyl ether. The resulting linear acetals were used for the synthesis of unsaturated rings via ring‐closing metathesis, in which the acetal carbon–a precursor for oxycarbenium or N‐sulfonyliminium ions, respectively–served as a reactive center for further introduction of functional groups. The products–unsaturated oxygen and nitrogen heterocyclic scaffolds–offer multiple opportunities for derivatization as illustrated with the synthesis of substituted dihydropyrans, chromenes, enantiopure tetrahydropyridines and an enantiomerically pure quinolizidine amino acid.

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[RhI(t-Bu2-boxate)(C2H4)2] spontaneously disproportionates to the mononuclear [RhII(t-Bu2-boxate)2], whereas [RhI(Ph2-boxate)(C2H4)2] is stable against disproportionation.

We have synthesized a new tetranuclear manganese cluster with a distorted cubanelike [Mn4O4]-core. High field magnetization experiments reveal an intramolecular antiferromagnetic coupling between the four manganese ions. We explain our results both qualitatively and quantitatively by a simple spin square model in terms of four equal antiferromagnetic exchange interactions in the core with coupling strengths of J =-1.69 K.