New amino-dithiaphospholanes and phosphoramidodithioites and their rhodium and iridium complexes

作者：Shejwalkar Pushkar; Sedinkin Sergey L; Bauer Eike B^*

来源：Inorganica Chimica Acta, 2011, 366(1): 209-218.

DOI：10.1016/j.ica.2010.11.006

• Amino-dithiaphospholanes
• Phosphoramidites
• Ligand design
• P ligands
• Organometallic syntheses
• Spectroscopy

New sulfur derivatives of phosphoramidite ligands were synthesized and the impact of the sulfur unit on the spectroscopic properties of their rhodium and iridium complexes was investigated. The new ligands Bn(2)NPSCH(2)CH(2)S(a)(P-S(a)) (Bn = benzyl, 4), Bn(2)NPSCHCHS(a)(CH(2))(3)C(a)H(2)(P-S(a))(C(a)-S(a)) (6) and Bn(2)NP(4-XC(6)H(4)-OMe)(2) (X = S, 7a; X = O, 7b) were converted to the rhodium and iridium complexes trans-[Rh(CO)Cl(L)(2)] (L = 4, 6, 7), [RhCl(COD)(L)] (L = 4, 6, 7), [IrCl(COD)(7a)] and [IrCl(2)Cp*(6)]. For comparison, some phosphoramidite complexes of these formulations also were synthesized. The new metal complexes were spectroscopically analyzed. For the carbonyl complexes, the nu(C=O) IR stretching frequencies were lower than for the corresponding phosphite and phosphoramidite ligands. The (1)J(PRh) coupling constants for the rhodium complexes with the new ligands were also smaller than for the respective phosphoramidite and phosphite complexes. Finally, the (1)J(PSe) coupling constants of the selenides of the new ligands were lower than those of the phosphoramidite ligands but higher than for PPh(3). The spectroscopic data reveal that the new thio ligands 4, 6 and 7a are more electron donating than phosphites and phosphoramidites but less electron donating than PPh(3).

• 出版日期2011-1-30