Reactions of boryloxymethyl- and hydroxymethylphosphines with amines

Pt‐ and Pd‐Complexes with Acyclic and Heterocyclic P‐Hydroxyaryl‐Substituted N‐Phosphanylmethyl Amino Acids RP(CH2NHR')2 and (RPCH2NR'CH2)2 – Evaluation of (P^O)M Chelate Formation

“…General: All reactions were carried out under argon, using Schlenk techniques. The synthesis of the ligands 1a – c and 6 was reported earlier;[3d] p ‐HOC 6 H 4 PH 2 and p ‐HOC 6 H 4 P(CH 2 OH) 2 . Pt(cod)Cl 2 and Pd(cod)Cl 2 were prepared by known procedures .…”

“…The ligands were synthesized by the classic route to phosphanylmethylamines but using amino acids instead of amines in the condensation step with PH‐functional phosphanes and formaldehyde or their addition products . Today various types of acyclic and heterocyclic phosphanylmethyl‐amino acid ligands and transition metal complexes are known, including a few representatives with SO 3 H instead of COOH groups and salts thereof . Alternative functionalization for modification and tuning of ligand properties comprises N‐protonation of ( R 2 N‐CH 2 ) 2 PR, RN(CH 2 PR 2 ) 2 or (diazadiphosphacyclooctane) ligands, , or the introduction of additional neutral amino, cationic NR + or N ‐acyl groups in heterocyclic P–C–N ligands with 3 or 4 N‐atoms in the ring (triazaphosphaadamantane and related types) .…”

“…[3d] Preliminary ligand screening with Ni(1,5‐cod) 2 and ethylene under pressure failed to detect efficient oligo‐ or polymerization catalysis on heating. The reason might be a preferred N,O‐[3b] or P,P'‐coordination of nickel by the o ‐hydroxyaryl‐substituted mono‐ and bis(P–C–N amino acid) ligands instead of the (P ^ O)Ni chelate structure, required for the conversion of ethylene to α‐olefin oligo‐ or polymers. [13c], To evaluate the preferred coordination modes of the P–C–N amino acids with pendant o ‐hydroxy groups at the P‐aryl substituent, as a basis for feasibility and possible further studies of their potential use, we studied some reactions of these ligands with group10 metal compounds, and report here on the results.…”

Synthesis of novel paracyclophanes with linear P,N-containing spacers

“…20) was also employed as a starting reagent since structurally similar anthranilic acid reacts with hydroxymethylphosphines as a secondary amine be cause of strong intramolecular hydrogen bonding between the carboxy and amino groups. 21 The starting diamines 1 and 4 were prepared by acid promoted reactions of formaldehyde with N methylaniline and anthranilic acid, respectively (see Refs 19,20). Earlier unknown bis[4 (3 pyridylmethyl)aminophe nyl]methane (2) and bis[4 (4 pyridylmethyl)aminophe nyl]methane (3) were synthesized by reduction of ap propriate diimines with NaBH 4 in ethanol as described for bis[4 (2 pyridylmethyl)aminophenyl]methane 22 (Scheme 1).…”

“…Compound 7 was obtained as a very viscous oil contain ing the target product (~85%) and unidentified oligo meric aminomethylphosphines. The positive ion MALDI TOF mass spectrum of com pound 5 showed a molecular ion peak with m/z 804 corresponding to the condensation product 3, 21 Like the spectrum of the reaction mixture, the 31 P NMR spectrum of compound 5 contained two closely spaced signals at δ -41.25 and -41. 30.…”