112220-49-2Relevant academic research and scientific papers
Synthetic methodologies for tripodal phosphines. The preparation of MeSi(CH2PPh2)3 and n-BuSn(CH2PPh2)3 and a comparison of their rhodium(I) andruthenium(II) coordination chemistry. The X-ray crystal structures of [ Rh(NBD){n-BuSn(CH2PPh2)3}](OTf) and [Rh(NBD){MeSi(CH2PPh2)3}](OTf)
Herold, Susanna,Mazzetti, Antonio,Venanzi, Luigi M.,Albinati, Alberto,Lianza, Francesco,et al.
, p. 215 - 232 (2008/10/08)
The preparation of the new tripodal ligands MeSi(CH2PPh2)3 (Si-triphos) and n-BuSn(CH2PPH2)3 (Sn-triphos) and their complexes of rhodium(I) of the type [Rh(NBD)(tripod)](OTf) (NBD=norbornadiene, OTf=triflate) and of ruthenium(II) of type [Ru(O2CCF3)2(tripod)], is reported. The coordination chemistry of the new tripodal phosphines, and in particular that of Sn-triphos, differs significantly from that of MeC(CH2PPh2)3 (triphos). A comparison of the X-ray structure of [Rh(NBD)(triphos)](OTf) with those of the new complexes [Rh(NBD)(Sn-triphos)](OTf) and [Rh(NBD)(Si-triphos)](OTf) shows that the steric requirements of the ligands RE(CH2PPh2)3 (E=C, Si and Sn), increase from the carbon to the tin compound. The coordination chemistry of ruthenium(II) indicates that, relative to triphos,Sn-triphos displays an enhanced steric bulk which, however, is not suff icient to stabilize the mononuclear, five-coordinate dichloro complexes.
Ruthenium(II) solvento complexes containing the tripod-like ligands MeC(CH2EPh2)3 (E = P or As) and their reactions with carbon monoxide. Crystal and molecular structure of [Ru2(μ-Cl)3(MeC(CH2PPh2) 3)2][BPh4]
Rhodes, Larry F.,Sorato, Carla,Venanzi, Luigi M.,Bachechi, Fiorella
, p. 604 - 610 (2008/10/08)
Treatment of [RuCl2(DMSO)4] with tripod [tripod = MeC(CH2EPh2)3, E = P (triphos) or As (triars)] yields [Ru2(μ-Cl)3-(tripod)2]Cl. In the case of triars the mononuclear intermediate [RuCl2(DMSO)(triars)] can be isolated. This condenses to the corresponding trichloro-bridged complex in MeOH. The chloride ligands of [Ru2(μ-Cl)3(tripod)2]Cl can be abstracted by AgCF3SO3 in MeCN to yield [Ru(MeCN)3(tripod)](CF3SO3)2. When the chloride abstraction is carried out in DMSO and above 100 °C, the products are [Ru(DMSO)3(tripod)](CF3SO3)2, whereas if the reaction is carried out below 100 °C, the mixed-solvent complexes [Ru(H2O)(DMSO)2(tripod)](CF3SO 3)2 are obtained. Reaction of the DMSO complexes with carbon monoxide gives the dicarbonyl triflate complexes [Ru(CF3SO3)(CO)2(tripod)](CF3SO 3). The X-ray diffraction study of a crystal of [Ru2(μ-Cl)3(tripod)2][BPh4] (orthorhombic, of space group Pccn and with a = 19.991 (8) A?, b = 18.388 (7) A?, c = 25.510 (10) A?, and Z = 4) is reported.
