Monica Helvia Perez-Temprano

• Chemistry
• Group Leader at Institute of Chemical Research of Catalonia

This report describes a combined experimental and computational investigation of the mechanism of C(sp(3))-N bond-forming reductive elimination from sulfonamide-ligated Pd(IV) complexes. After an initial experimental assessment of reactivity, we used ZStruct, a computational combinatorial reaction finding method, to analyze a large number of multis...

This article describes an investigation of C(sp(3))-O bond-forming reductive elimination reactions from Pd(IV) complexes. Phenoxide, acetate, difluoroacetate, dimethylphosphate, tosylate, and nitrate nucleophiles are shown to participate in this reaction. In all cases, C(sp(3))-O bond formation occurs with high selectivity over potentially competin...

Experiments on palladium-catalyzed cross-coupling of [AuMe(PPh3)] with aryl iodides show that Ar-Ar homocoupling products are the main product or an abundant byproduct of the reaction. The percentage of cross-coupling product is higher for aryls with a larger σp Hammet parameter. The scrambling of organic groups via bimetallic intermediates explain...

This communication describes the design of a model system that allows direct investigation of competing sp(3)-C-N and sp(3)-C-F bond-forming reductive elimination from a Pd(IV) fluoro sulfonamide complex. The reductive elimination selectivity varies dramatically as a function of reaction additives. A mechanism is proposed that provides a rationale...

It's the second step that counts: arylation of Pd by Au takes place through transition states and intermediates featuring strong Au⋅⋅⋅Pd metallophilic interactions. However, the aryl transfer from [AuArL] to [PdArClL(2)] is thermodynamically disfavored and will not occur unless an irreversible Ar-Ar coupling from [PdAr(2)L(2)] follows.

Bimetallic catalysis refers to homogeneous processes in which either two transition metals (TM), or one TM and one Group 11 (G11) element (occasionally Hg also), cooperate in a synthetic process (often a C-C coupling) and their actions are connected by a transmetalation step. This is an emerging research area that differs from the isolated or tande...

The kinetics of the Stille reaction between C6Cl2F3I and PhCCSnBu3 have been studied for the whole catalytic system and for transmetalations as separate steps. The use of (trifluorodichlorophenyl)palladium derivatives slows down the reactions and allows for the observation of the intermediates cis- and trans-[Pd(C6Cl2F3)I(PPh3)2]. The first is form...

A convenient method for the quick preparation of SnBu2RX (Bu = n-Bu) has been developed using microwave irradiation and column chromatography in acidic alumina. The method can be a good alternative particularly for easy and quick preparation of small amounts for test purposes and, in general, for the synthesis of compounds that cannot be purified b...

A DFT study of R-R reductive elimination (R = Me, Ph, vinyl) in plausible intermediates of Pd-catalyzed processes is reported. These include the square-planar tetracoordinated systems cis-[PdR(2)(PMe(3))(2)] themselves, possible intermediates cis-[PdR(2)(PMe(3))L] formed in solution or upon addition of coupling promoters (L = acetonitrile, ethylene...

A study of the reaction of cis-[PdRf2(AsPh3)2] (Rf = 3,5-C6Cl2F3) with ISnBu3 (that is the reversal of the natural Stille reaction of [PdRfI(AsPh3)2] with RfSnBu3) allows for the observation of cis-[PdRf2(AsPh3)(ISnBu3)], the expected intermediate from a cyclic transmetalation in the direct Stille reaction, thus providing experimental support to th...