CÁMPORA PÉREZ , Juan

Monomeric alkoxo complexes of the type [(iPrPCP)M-OR] (M = Ni or Pd; R = Me, Et, CH2CH2OH; iPrPCP = 2,6-bis(diisopropylphosphino)phenyl) react rapidly with CO2 to afford the corresponding alkylcarbonates [(iPrPCP)M-OCOOR]. We have investigated the reactions of these compounds as models for key steps of catalytic synthesis of organic carbonates...

Dialkylmagnesium compounds [MgR2L2] (R = n-Bu, L = none or R = Bn, L = THF) react with 2,6-bis(imino)pyridines (BIP) to afford different types of Mg(II) alkyl complexes, depending on the nature of R. For R = n-Bu, thermally stable products resulting from selective alkyl transfer to the pyridine nitrogen (N1) atom are obtained. However, NMR...

Ligand exchange reactions have been used for the synthesis of metallacyclic complexes of Ni and Pd of the type [M[upper bond 1 start](CH2CMe2-o-C6[upper bond 1 end]H4)(P–N)], where P–N is the phosphinito-imine ligand P(iPr)2OC(Me)[double bond, length as m-dash]N(2,6-C6H3(iPr)2. The protic acid [H(OEt2)(BAr′4)] (Ar′ = 3,5-C6H3(CF3)2) selectively...

The dihapto coordination of two molecules of carbon dioxide to a square-planar MoP2(P-P) fragment (P=monodentate-, P-P=bidentate phosphi- ne ligands) can occur in several ways giving rise to different conformers. Compounds of this type have been prepared and their spectroscopic proper- ties investigated by variable temperature 'H and 31P NMR...

The outcome of the reaction of manganese(II) dialkyls with 2,6-bisiminopyridine (BIP) ligands is dramatically altered by the presence of very small amounts of oxygen (< 0.5 mol %), leading to binuclear species. These arise from the dimerization of the initial product, a Mn(II) 4-alkyl-2,6-bisiminodihydropyridinate alkyl complex. Cleavage of the...

Neophylpalladium complexes of the type [Pd(CH(2)CMe(2)Ph)(N-O)(L)], where N-O is picolinate or a related bidentate, monoanionic ligand (6-methylpyridine-2-carboxylate, quinoline-2-carboxylate, 2-pyridylacetate or pyridine-2-sulfonate) and L is pyridine or a pyridine derivative, efficiently catalyze the oxidation of a range of aliphatic,...

The 1,4-dihydropyridinate complex [(4-BnHBIP)Zn(Bn)], readily available through the highly selective reaction of a 2,6-bis(imino)pyridine ligand with dibenzylzinc, contains two distinct reactive centers. One of them is the σorganometallic benzylzinc moiety, which reacts with weak protic acids (e.g., water and methanol) to release the free...

The first complexes containing imidazolium-2-amidinates as ligands (betaine-type adducts of imidazolium-based carbenes and carbodiimides, NHC-CDI) are reported. Interaction of the sterically hindered betaines ICyCDIDiPP and IMeCDIDiPP [both bearing 2,6-diisopropylphenyl (DiPP) substituents on the terminal N atoms] with Cu(I) acetate affords...

Nickel and palladium methoxides [((iPr)PCP)M-OMe], which contain the (iPr)PCP pincer ligand, decompose upon heating to give products of different kinds. The palladium derivative cleanly gives the dimeric Pd(0) complex [Pd(μ-(iPr)PCHP)]2 ((iPr)PCHP = 2,6-bis(diisopropylphosphinomethyl)phenyl) and formaldehyde. In contrast, decomposition of...

Diorganozinc compounds (ZnR2) with R = CH2Ph or CH2CH[double bond, length as m-dash]CH2 react with 2,6-bisiminopyridines (iPrBIP) to afford thermally stable dihydropyridinate(−1) complexes, and do not react if R = CH2SiMe3 or CH2CMe2Ph. NMR studies reveal that dibenzylzinc binds iPrBIP at −80 °C, yielding the unstable complex...

A series of complexes of the type [(iPrPCP)M-L] (M = Ni, Pd), containing the 2,6-bis(diisopropylphosphinomethyl)phenyl (iPrPCP) pincer ligand and simple monoanionic ligands L (F, Cl, Br, H, Me, Ph, NO3, and OTf), have been synthesized and characterized. The fluoride derivatives [(iPrPCP)M-F] were prepared from the halides [(iPrPCP)M-X] (M = Ni,...

The reactions of the pincer hydroxide complexes [(iPrPCP)M(OH)] (M=Ni, Pd) with dimethyl carbonate (DMC), and a set of organic electrophiles including benzaldehyde have been investigated in the context of our ongoing investigation on the synthesis of alkyl carbonates from CO2 and alcohols. The final outcome of such reactions is diverse, but for...