CONEJERO , Salvador

The ambiguous bonding situation of σ-E−H (E=Si, B) complexes in transition metal compounds has been rationalized by means of Density Functional Theory calculations. To this end, the combination of the Energy Decomposition Analysis (EDA) method and its Natural Orbital for Chemical Valance (NOCV) extension has been applied to representative...

Platinum complexes have been often considered as the least reactive of the group 10 triad metals. Slow kinetics are behind this lack of reactivity but, still, some industrially relevant catalytic process are dominated by platinum compounds and sometimes different selectivities can be found in comparison to Ni or Pd. Nevertheless, during the...

In this Perspective we discuss the ability of transition metal complexes to activate and cleave the Si–H and B–H bonds of hydrosilanes and hydroboranes (tri- and tetra-coordinated) in an electrophilic manner, avoiding the need for the metal centre to undergo two-electron processes (oxidative addition/reductive elimination). A formal...

The low-electron-count cationic platinum complex [Pt(ItBu')(ItBu)][BAr], 1, interacts with primary and secondary silanes to form the corresponding σ-SiH complexes. According to DFT calculations, the most stable coordination mode is the uncommon η-SiH. The reaction of 1 with EtSiH leads to the X-ray structurally characterized 14-electron Pt...

The reaction of tri-coordinated boranes (derived from dioxaborolanes and diazaborolanes) with cyclometalated low-electron count platinum complexes [Pt(NHC')(NHC)][BArF] (NHC=ItBuiPr, IMes, IMes*) led, at low temperature, to the formation of the corresponding σ-BH species. Some of these species have been characterized by X-Ray diffraction...

Cationic five-coordinate Pt(IV) alkyl complexes stabilized by bulky N-heterocyclic carbenes have been isolated and fully characterized. Related species have been postulated as key intermediates in carbon–heteroatom coupling reactions and most particularly in Shilov-type chemistry. The alkyl groups exhibit a pronounced electrophilic character...

The low electron count Pt(II) complexes [Pt(NHC′)(NHC)]- [BArF] (where NHC is a N-heterocyclic carbene ligand and NHC′ its metalated form) react with tertiary hydrogermanes HGeR3 at room temperature to generate the 14-electron platinum(II) germyl derivatives [Pt(GeR3)(NHC)2][BArF]. Low-temperature NMR studies allowed us to detect and...

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(II) complex [Pt(ItBuiPr′)(ItBuiPr)][BArF], 1, with tricoordinated boranes HBR2. X-ray diffraction studies provided structural snapshots of the sequence of reactions involved in the process. At low temperature, we...

N-Heterocyclic Thiones (NHT) proved to be efficient ligands for the stabilization of small platinum nanoparticles (1.3-1.7 nm), synthesized by decomposition of [Pt(dba)2], under a H2 atmosphere, in the presence of variable sub-stoichiometric amounts of the NHT. Full characterization by means of TEM, HR-TEM, NMR, ICP, TGA and XPS have been...