Biologically inspired phosphino platinum complexes

The Outer-Coordination Sphere: Incorporating Amino Acids and Peptides as Ligands for Homogeneous Catalysts to Mimic Enzyme Function

“…When two equivalents of the amine were added, the octahedral P 2 N 2 was formed. Eight-membered ring formation is not observed for standard amino acids, only for the non natural aniline derivatives, as observed by Karasik and others (89)(90)(91)(92).…”

“…More recently, amino acid containing PN 2 and P 2 N 2 ligands and their metal complexes have been prepared and tested as catalysts for hydrogenation and electrocatalytic hydrogen production by Shaw and coworkers (92). Amino acids and esters of glycine were used to make PN 2 -type ligands that were coordinated to PtCl 2 or Pt(CH 3 ) 2 .…”

Phospha-Mannich reactions of RPH2, R2PH, and R3P

“…Entry R R' Yield, % d P , ppm Me 73 [16] -68.3 (C 6 D 6 ) 63 [17,18] -60 (C 6 H 6 ) 43 [17,18] -60 (C 6 H 6 ) 40 [18] -60 (C 6 H 6 ) 42 [17,18] -60 (C 6 H 6 ) 65 [19] -56.1 (CD 3 OD) ~ 75 [20] -59.8 (MeOH), -60.4 (H 2 O) ~ 75 [20] -59.8 (MeOH), -60.4 (H 2 O) 62, [21] 67 [19] -55.4 (MeOH), -60.1 (CD 3 OD), -61.0 (H 2 O) 84 [21] -55.5 (MeOH), -62.1 (H 2 O) 40 [22] -61.5 (C 6 H 6 ) 38 [23,24] -50.0 (CD 3 OD), -55 (basic D 2 O) 76 [25] -66.3 (D 2 O) 74 [25] -75.6 (basic D 2 O) 73 [25] -76.2 (basic D 2 O) 16 77 [25] -74.2 (basic D 2 O) 17 68 [25] -69.0 (basic D 2 O) 18 84 [25] -70.0 (basic D 2 O) 19 40 [26] -39.9 (-) 20 72 [21] -57.7 (MeOH), -66.0 (H 2 O) 21 63 [21] -54.4 (MeOH), -66.1 (H 2 O) 22 46 [21] -69.7 (MeOH), -77.1 (H 2 O) 23 54 [21] -68.7 (MeOH), -77.1 (H 2 O) 24 Me 73 [27] -47.6 (CDCl 3 )…”

Synthesis of platinum, palladium and rhodium complexes of α-aminophosphine ligands

“…In the reaction of Pt II (cod)X 2 precursors with 1,3-diaza-phosphacyclohexanes incorporating two glycine or glycinate moieties, the corresponding cis complexes were formed (Scheme 43). 79 Depending on the functionality (acid or ester), the complexes were soluble in water or in organic solvents, respectively. The structure of the free acid was confirmed by X-ray diffraction analysis.…”