New Diphosphane Ligands Based on Bisphenol A Backbones − Synthesis and Coordination Chemistry

Abstract

A series of easily accessible diphosphane compounds 1−4, based on bisphenol A derived backbones, has been prepared. A straightforward two‐step synthetic route has been employed to obtain these new ligands in good yields from cheap starting materials. Molecular structures for both compound 2 and its oxidized form (5·H2O) have been determined and are discussed in detail. The coordination of ligand 2 to palladium, platinum, and rhodium precursors has been studied by NMR spectroscopy as well as X‐ray crystallography. The molecular structures of the face‐to‐face dimeric species [{PdCl(CH3)(2)}2] (6), [{PtCl2(2)}2] (7), and [{RhCl(CO)(2)}2] (8) are described in detail. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Versatile Phosphite Ligands Based on Silsesquioxane Backbones

“…We were therefore interested to study the coordination with a third metal species, the rhodium dimer [Rh(m-Cl)(CO) 2 ] 2 . As we [16,34,35] and others [36] have previously reported, the corresponding RhCl(CO)(P) 2 -complexes normally exhibit trans-coordination of two phosphorus moieties, although some cis complexes have also been described.…”

Synthesis, coordination studies and redox properties of a novel ditertiary phosphine bearing two ferrocenyl groups

“…The torsion twist angles about the Cp cent Á Á ÁFeÁ Á ÁCp cent in 8 are 13.0°and 3.4°while the FeÁ Á ÁFe separations are 6.987 Å [Fe(1)Á Á ÁFe (2) (2a)]. Between adjacent trans-RhCl(CO) fragments the RhÁ Á ÁRh separation is 6.199 Å and is considerably shorter than found in a related dimeric rhodium(I) complex containing a diphosphine ligand based on bisphenol [9.0005(11) Å] [50]. The structure of 8 represents the first crystallographically characterised metallacycle containing an Rh 2 Fe 4 arrangement of metal centres.…”

Highly Selective Cobalt‐Catalyzed Hydrovinylation of Styrene

“…X-ray crystallographic studies reveal that in the solid state BPC 6 -phos (8) coordinates in a bridging dimeric fashion in complexes of PdCl 2 , PtCl 2 and Rh(CO)Cl. [16] DPEphos (6) and Xantphos (7) led to significantly lower activities, as the conversion reached only 24 and 9% conversion, respectively, after 90 min of reaction time (entries 7 and 8). Cobalt complexes bearing the heterodonor ligands dppn and dppo perform even better than Co(1)Cl 2 , with Co(12)Cl 2 being slightly more active than Co(11)Cl 2 , giving 100% conversion after 30 min (entry 14).…”