Exploring Rhodium(I) Complexes [RhCl(COD)(PR₃)] (COD = 1,5-Cyclooctadiene) as Catalysts for Nitrile Hydration Reactions in Water: The Aminophosphines Make the Difference

Abstract

Several rhodium(I) complexes [RhCl(COD) (PR 3 )

Cymene‐Osmium(II) Complexes with Amino‐Phosphane Ligands as Precatalysts for Nitrile Hydration Reactions

“…As shown in entries 16 and 17 (Table ), both complexes were active in the process delivering benzamide in 82 and 74% GC yield, respectively, after 3 h, values that are clearly lower to that obtained with [OsCl 2 ( η 6 ‐ p ‐cymene){PPh 2 (NMe 2 )}] ( 5 a ) under identical experimental conditions (97% GC yield; entry 13). Further evidences of the superior reactivity of 5 a were gained when the known Rh(I) [RhCl(COD){PPh 2 (NMe 2 )}] ( 13 ; COD=1,5‐cyclooctadiene) and the novel Pt(II) cis ‐[PtCl 2 {PPh 2 (NMe 2 )} 2 ] ( 15 ) complexes (see Figure ) were employed as catalysts (1 mol%), since in these cases only 1–3% of benzamide was formed after 3 h of heating at 100 °C (entries 18 and 19 in Table ) . Concerning the synthesis of cis ‐[PtCl 2 {PPh 2 (NMe 2 )} 2 ] ( 15 ), it was isolated in 75% yield from the reaction of 1,5‐cyclooctadiene‐Pt(II) precursor [PtCl 2 (COD)] ( 14 ) with two equivalents of the amino‐phosphane 2 a (details are given in the Supporting Information).…”

Copper(II) and Sodium(I) Complexes based on 3,7‐Diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane‐5‐oxide: Synthesis, Characterization, and Catalytic Activity

“…Among the large family of open‐cage PTA derivatives, 3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane (DAPTA) is a relevant one (Figure ), and its binding capacity has been intensively studied for the Cu, Ru, Rh, Pd, Pt, and Au transition metals to produce complexes that are used mainly for biological applications and, to a lesser extent, for catalysis . The DAPTA ligand usually exhibits the P‐coordination mode to the metal center, and recently, the N‐coordination mode was also reported .…”

“…[7][8][9][10] Among the large family of open-cage PTAd erivatives, [2,11] 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) is ar elevant one (Figure 1), [11a, 12] and its binding capacity has been intensively studied for the Cu, Ru, Rh, Pd, Pt, and Au transition metals to produce complexes that are used mainly for biological applications [13][14][15][16] and, to al esser extent, for catalysis. [17][18][19][20] The DAPTAl igand usually exhibits the P-coordination modet ot he metal center, [12][13][14][15][20][21][22][23] and recently,t he N-coordination mode wasa lso reported. [17] Although DAPTAh as two coordination sites from the acetyl oxygen atoms, the O-coordination modeo fD APTAhas not yet been reported.…”

Rhodium Pyrrolylphosphine Complexes as Highly Active and Selective Catalysts for Propene Hydroformylation: The Effect of Water and Aldehyde on the Reaction Regioselectivity

“…Rh complexes with tripyrrolylphosphine, [RhCl(cod)(PPyr 3 )] (cod=cyclooctadiene), [HRhCO(PPyr 3 ) 3 ], and HRh(PPyr 3 ) 4 have also been applied in the hydrogenation of organonitriles, cyclic olefins, and aromatics …”