Heterocyclic Phosphines with P-C-X Fragments (X=O, N, P)

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

“…The assignment of the 31 P resonance to the κP and κ 2 P,Oligands is based on the diagnostic crosspeaks with H3 and the more upfield absorbing H3′ (o-position to O -) in the PH-COSY spectrum of the DMF solvate of 9. The cis-configuration of the Pt complexes is proved by large 1 J PtP coupling constants, ranging for the new compounds from 2900 to 3600 Hz, and for the mixed κ 1 (P^OH)/κ 2 (P^O -) coordinated Pt and Pd complexes by small 2 J PP′ values (5)(6)(7)(8)(9)(10)(11)(12)(13)(14). For trans-PPtP isomers the trans-influence-sensitive 1 J PtP values should be smaller than 2800 Hz and the diagnostically valuable 2 J PP′ couplings much larger than observed (for PC 3 -type ligands ca.…”

“…[2] 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. [3][4][5] Alternative functionalization for modification and tuning of ligand properties comprises Nprotonation of (R 2 N-CH 2 ) 2 PR, RN(CH 2 PR 2 ) 2 or (diazadiphosphacyclooctane) ligands [4,6,7] 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). [8][9][10] Such compounds have been used for highly efficient biomimetic Ni-catalyzed hydrogenations [4,6] or to generate cationic, zwitterionic or amide-functionalized heterocyclic ligands for anticancer studies of Pt and other transition metal complexes.…”

“…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) .…”

“…5 Hz, 2 H, 9′-H), 8.37 (superimposed m, J = 3-4 Hz, 2 H, NH′); 3.28 (s, 4.5 H, MeOH), 3.2-3.8 (superimposed vbr s, OH, H 2 O), 13.0 (vbr s, 4 H, CO 2 H). 13 C{ 1 H} NMR ([D 7 ]DMF): δ = 38.99 (d, 1 J = 41.9 Hz, 2 PC ( ′ ) H 2 N), 39.97 (d, 1 J = 41.6 Hz, 2 PC ( ′ ) H 2 N),49.3 (MeOH), 112.15, 112.27 (superimposed s, each 2 C q -8 and -8′ and 2 C-12 and -12′), 112.63 (superimposed d, 1 J = 48-57 Hz (uncertain), C q -1 or -1′), 113.01 (d, 1 J = 59.4 Hz, C q -1 or -1′), 115.86, 116.10 (2s, 2 C-10, 2 C-10′), 116.28, 117.37 (2 br s, C-3, C-3′), 117.95 (br unresolved d or m, C-5 or -5′), 120.84 (d, 3 J = 9.2 Hz, C-5 or C-5′), 132.40 (s, 2 C-9, 2 C-9′), 132.24, 134.13, 134.14, 134.71 (4 s, C-4, C-4′, C-6, C-6′), 134.85 (s, 2 C-11, 2 C-11′), 150.68, 150.75, 151.06, 151.13 (4 s, 2 C q -7, 2 C q -7′), 160.93 (s, C q -2), 170.40, 170.71 (4 CO 2 H), 178.18 (d, 2 J = 13.7 Hz, C q -2′).…”

Pyridyl Containing 1,5-Diaza-3,7-diphosphacyclooctanes as Bridging Ligands for Dinuclear Copper(I) Complexes

“…Recent works illustrate a wide utilization of Ni II complexes of 1,5‐diaza‐3,7‐diphoshpacycloctanes as catalysts in the electrochemical hydrogen production , . Profound interest in these type of ligands grows due to possibility of their simple tuning by the introduction of functionalized substituents to the amine or phosphine moieties . Despite of the wealth of information only two papers dedicated to P,P‐chelate copper complexes based on these ligands were published, and no data devoted to the luminescence of these complexes has been reported so far.…”