Rhodium(I) carbonyl complexes of mono selenium functionalized bis(diphenylphosphino)methane and bis(diphenylphosphino)amine chelating ligands and their catalytic carbonylation activity

Oxidative addition of different electrophiles with rhodium(I) carbonyl complexes of unsymmetrical phosphine–phosphine monoselenide ligands

“…35 The elemental (C, H, Cl) analysis data of the complexes 1a-d match well with the calculated ones ( Table 1). The monocarbonyl complex 1a shows a ν(CO) band at around 1977 cm −1 (Table 2), while 1b-d exhibit two equally intense ν(CO) bands in the range 1984-2067 cm −1 , indicating cis disposition of the two terminal carbonyl groups.…”

“…37,40 The ν(PSe) band of 1a occurs at a Our earlier report. 35 513 cm −1 , which is significantly lower than the free ligand a {ν(PSe) = 527 cm −1 ) and thus indicates the chelate formation in the complex 1a through the Rh-Se bond. In contrast, the ligands b-d in the complexes 1b-d coordinate to the metal center through their tertiary phosphorus atom only, which is corroborated by the IR spectra (Table 2) of the ν(PSe) stretchings which are close to the corresponding free ligand bands.…”

“…In contrast, a few reports exist on phosphine-phosphine monoselenide complexes. 11,15,29 -34 Recently, Dutta et al 35 reported on the rhodium carbonyl complexes of the types [Rh(CO)Cl(Ph 2 PCH 2 P(Se)Ph 2 )] and [Rh(CO)Cl(Ph 2 PN(CH 3 )P(Se)Ph 2 )] and their catalytic activity. Substantial activity has been aroused on the synthesis of rhodium carbonyl complexes because of their versatile application in homogeneous catalysis, such as carbonylation of alcohols.…”

Two Carbonylations of Methyl Iodide and Trimethylamine to Acetic acid and N,N-Dimethylacetamide by Rhodium(I) Complex: Stability of Rhodium(I) Complex under Anhydrous Condition

“…First of all, it was observed that there were two carbonylation routes of trimethylamine and methyl iodide and the carbonylation rate of trimethylamine was faster than that of methyl iodide. It is concluded that increasing electron density at the rhodium center by different ligands consequently enhances the overall rate of acetic acid formation by facilitating the oxidative addition of methyl iodide [29][30][31][32][33] and electron density at the rhodium center was increased by monodentate amine ligands [12].…”

“…Therefore, it is suggested that substitution of iodo ligand on the complex [Rh(COMe)(CO)2I2 (NMe3) (1) was extremely slow [6], it was observed that the carbonylation rate of trimethylamine was faster than that of methyl iodide in the reaction since increasing electron density at the rhodium center by trimethylamine ligand enhanced the oxidative addition rate of methyl iodide [29][30][31][32][33]. Therefore, from the carbonylation of trimethylamine in the presence of hydroxide anion or limited water, DMAC was obtained as the major product (Figure 1).…”