0000000000286371
AUTHOR
Isabel Rojo
Chelation of a proton by oxidized diphosphines
Abstract The chelation of a proton by oxidized diphosphines is studied for the first time both experimentally and theoretically. As a proof of concept the rare case where two different H-bond systems exist in one compound, H[7,8-(OP i Pr 2 ) 2 -7,8- nido -C 2 B 9 H 10 ] is reported. Based on NBO, QTAIM and ELF calculations, the P–O⋯H + ⋯O–P interactions were characterized as strong hydrogen bonds.
Intramolecular Communication in Anionic Oxidized Phosphanes through a Chelated Proton
Oxidation of the 1,2-(PR2 )2 -1,2-closo-C2 B10 H10 (R=Ph, iPr) platform with hydrogen peroxide in acetone is a two-step procedure in which partial deboronation of the closo cluster and oxidation of the phosphorus atoms occur. Based on NMR spectroscopic and kinetic data, we demonstrate that the phosphorus atoms are oxidized in the first step, followed by cluster deboronation. DFT calculations and natural-bond orbital (NBO) analysis were used to obtain insight into the electronic structures of diphosphane ortho-carborane derivatives.
Synthesis and coordinating ability of an anionic cobaltabisdicarbollide ligand geometrically analogous to BINAP.
The anionic chelating ligand [1,1'-(PPh 2 ) 2 -3,3'-Co(1,2-C 2 B 9 H 1 0 ) 2 ] - has been synthesized from [3,3'-Co(1,2-C 2 B 4 H 1 1 ) 2 ] - in very good yield in a one-pot process with an easy work-up procedure. The coordinating ability of this ligand has been studied with Group 11 metal ions (Ag, Au) and with transition-metal ions (Pd, Rh). The two dicarbollide halves of the [1,1'-(PPh 2 ) 2 -3,3'-Co(1,2-C 2 B 9 H 1 0 ) 2 ] - ligand can swing about one axis in a manner analogous to the constituent parts of BINAP and ferrocenyl phosphine derivatives. All these ligands function as hinges, with the most important property in relation to the coordination requirements of the metal being the P…
Relevance of the Electronegativity of Boron inη5-Coordinating Ligands: Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide[3,3′-Co(1,2-C2B9H11)2]− Clusters
Regioselective monoalkylation and monoarylation in cobaltabisdicarbollide clusters has been achieved starting from Cs[8-I-3,3'-Co(1,2-C 2 B 9 H 1 0 )(1',2'-C 2 B 9 H 1 1 )] by cross-coupling reactions between a B-I fragment andan appropriate Grignard reagent in the presence of a Pd catalyst and CuT. A considerable number of monoalkylated and monoarylated derivatives have been synthesized, which allowed study of the influence of boron in metallocene-type ligands and the effect of alkyl and aryl substituents on boron in boron anionic clusters. Experimental data from UV/ Vis spectroscopy, E 1 / 2 measurements, and X-ray diffraction analysis, and supported by EHMO and ab initio analyses, indica…
Formation of Bridging Alkene and Conjugated Dialkenes Exclusively Generated from Alkynes on the [3,3‘-Co(1,2-C2B9H11)2]- Platform. The Unique Hydroboration Role of [3,3‘-Co(1,2-C2B9H11)2]-
The unprecedented metal-mediated transformation of an alkyne into a B,B' bridging alkene is reported. Also, the unprecedented synthesis of a conjugated dialkene derivative of [3,3'-Co(1,2-C2B9H11)2]- generated only from an alkyne, contrary to the usual case where an alkyne and an alkene are needed, is described. This has been possible through the singular capacity of a B-H to produce hydroboration.
Methylation and Demethylation in Cobaltabis(dicarbollide) Derivatives
B(8)−R and B(8‘)−R (R = alkyl) disubstituted derivatives of the cobaltabis(dicarbollide) anion [3,3‘-Co(C2B9H11)2]- are reported. The synthesis was achieved by application of a modified Kumada reac...
Relaxed but highly compact diansa metallacyclophanes.
A series of monoansa [μ-1,1′-PR-3,3′-Co(1,2-C2B9H10)2]− and diansa [8,8′-μ-(1″,2″-benzene)-μ-1,1′-PR-3,3′-Co(1,2-C2B9H9)2]− (R = Ph, tBu) cobaltabisdicarbollidephanes have been synthesized, characterized and studied by NMR, MALDI-TOF-MS, UV-visible spectroscopy, cyclic voltammetry, and DFT calculations. Single crystal X-ray diffraction revealed a highly relaxed structure characterized by the title angle α of 3.8° ([7]−), this being the smallest angle α for a metallacyclophane. In such compounds, the metal-to-phosphorus distance is less than the sum of their van der Waals radii. The availability of a phosphorus lone pair causes an electron delocalization through the metal, as shown by the ab…