Since Tolman’s review1, a landmark in organometallic chemistry, the donor-acceptor properties of phosphines have been subject of intense experimental and theoretical studies. Most part of researches were devoted to mono-phosphines but only few studies to chelating di-phosphine2. The assumption that the effects of substituent on phosphorus in bidentate phosphines is the same as in the monodentate ones is not obvious. We have investigated the electronic and steric properties of a series of atropisomeric aryl and heteroaryl phosphines by the synthesis and characterization of the corresponding nichel dicarbonyl and Rhodium chloro carbonyl complexes and determined the structure of [BitiampNi(CO)2] by single crystal X-ray determination.We will discuss the linear correlations found among the IR stretching frequencies of the complexes and the pKa or E° of the free ligands and with the catalytic activities in hydrogenation of olefins.
Donor-acceptor properties of atropisomeric diphosphines in Nickel di-carbonyl and Rhodium-chloro-carbonyl complexes
M. Fusè;D. Zerla;E. Cesarotti;R. Gandolfi;
2014-01-01
Abstract
Since Tolman’s review1, a landmark in organometallic chemistry, the donor-acceptor properties of phosphines have been subject of intense experimental and theoretical studies. Most part of researches were devoted to mono-phosphines but only few studies to chelating di-phosphine2. The assumption that the effects of substituent on phosphorus in bidentate phosphines is the same as in the monodentate ones is not obvious. We have investigated the electronic and steric properties of a series of atropisomeric aryl and heteroaryl phosphines by the synthesis and characterization of the corresponding nichel dicarbonyl and Rhodium chloro carbonyl complexes and determined the structure of [BitiampNi(CO)2] by single crystal X-ray determination.We will discuss the linear correlations found among the IR stretching frequencies of the complexes and the pKa or E° of the free ligands and with the catalytic activities in hydrogenation of olefins.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
