ChemInform Abstract: Sterically Demanding, Sulfonated, Triarylphosphines: Application to Palladium-Catalyzed Cross-Coupling, Steric and Electronic Properties, and Coordination Chemistry

Autor: Raluca Craciun, Jason M. Spruell, Kevin P. O’Halloran, Elizabeth C. Western, Lucas Moore, Kevin H. Shaughnessy, David A. Dixon
Rok vydání: 2008
Předmět:
Zdroj: ChemInform. 39
ISSN: 1522-2667
0931-7597
DOI: 10.1002/chin.200829089
Popis: Tri(2,4-dimethyl-5-sulfonatophenyl)phosphine trisodium (TXPTS·Na3) and tri(4-methoxy-2-methyl-5-sulfonatophenyl)phosphine trisodium (TMAPTS·Na3) both provide more active catalysts for Suzuki and Sonogashira couplings of aryl bromides in aqueous solvents than tri(3-sulfonatophenyl)phosphine trisodium (TPPTS·Na3). In the Heck coupling, TXPTS·Na3 provides the most effective catalyst system. Cone angles determined from DFT-optimized structures show that both TXPTS·Na3 (206°) and TMAPTS·Na3 (208°) are significantly larger than TPPTS·Na3 (165°). The identity of the counterion had a significant effect on the calculated cone angles for these ligands. The electronic properties of these ligands determined by the CO stretching frequencies of trans-RhL2(Cl)CO complexes were identical, although calculated electronic parameters suggest subtle differences between these ligands. Similar to TPPTS·Na3, both TXPTS·Na3 and TMAPTS·Na3 react with Pd(OAc)2 in aqueous solvents to give LnPd0 complexes and the corresponding phosph...
Databáze: OpenAIRE
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