Phosphoric triamides. 31Phosphorus NMR chemical shift as a function of the P–N bond characteristics

Abstract

Six phosphoric triamides in which amide nitrogens are incorporated into an increasing number (from 0 to 3) of the 1,3,2-diazaphospholidin-2-one rings have been prepared and their crystal structures have been determined. The structural changes from the non-cyclic to the mono-, di-and tri-cyclic systems result in the decrease of the N᎐P᎐N bond angles and the increase of the P᎐N bond distance. These changes are paralleled by a strong deshielding of the 31 P nucleus, leading to an exceptionally high P value for the tricyclic derivative. The P -structural parameters relationship is discussed in terms of the changes in hybridization of phosphorus and the variation in the P᎐N bond order.

Two newXP(O)[NHC(CH3)3]2phosphoramidates, withX= (CH3)2N and [(CH3)3CNH]2P(O)(O)

“…In compounds having an (N)P(O)(NH) 2 skeleton (six structures), three different linear arrangements were observed: (i) formed through POÁ Á ÁH-N hydrogen bonds, with one N-H unit not involved in hydrogen bonding (Fig. 1a) (NUVROL;Bourne et al, 1998); (ii) with molecules linked by an R 1 2 (6) ring ( Fig. 1b) (MIFYIJ; Gholivand et al, 2002); (iii) formed via an R 2 2 (8) ring ( Fig.…”

Synthesis of Differently Substituted tacn‐Based Ligands: Towards the Control of Solubility and Electronic and Steric Properties of Uranium Coordination Complexes

“…Data reproducibility was carefully checked on independently synthesized and measured samples. The ditosylate of ethylene glycol,27 1,4,7‐tri‐4‐tosyl‐1,4,7‐triazaheptane,28 1,4,7‐tri‐4‐tosyl‐1,7‐disodio‐1,4,7‐triazaheptane,29 1,4,7‐tri‐4‐tosyl‐1,4,7‐triazacyclononane,29 1,4,7‐triazacyclononane trihydrochloride,30 and 1,4,7‐triazacyclononane31 were synthesized according to published procedures.…”

Phosphoramidates: Molecular Packing and Hydrogen Bond Strength in Compounds Having a P(O)(N)n(O)3-n (n = 1, 2, 3) Skeleton

“…In compounds having an (N)P(O)(NH) 2 skeleton, three different linear arrangements were observed: a) through P(O)···H-N hydrogen bonds in which one N-H unit doesn't cooperate in H-bonding (NUVROL [107], Scheme 27 and HIVLII [67], Scheme 28), b) through R 2 1 (6) (in [(CH 3 ) 2 [62] and the compound with refcode IKASAP [47], Scheme 29 (bottom)), two latter cases via P(O)···(H-N)(H-N) grouping in which the phosphoryl oxygen atom acts as a double-H acceptor.…”

“…The single crystal X-ray determinations were performed for [R 1 R 2 N] = NHCH 3 (KABVAL) [93], N(CH 3 ) 2 (POTJAJ) [94], NHC(CH 3 ) 3 (KABVEP) [93], NHC 6 H 5 (KEQLUO) [95], NHCH 2 C 6 H 5 (TOKXIB) [96] and NHC 6 H 4 (4-OCH 3 ) (WAWNIS) [97] and also for the substituents shown in Scheme 17 [98][99][100][101][102][103][104][105]. Moreover, a few other phosphoramide compounds which each contains a triamido moiety (like for example compounds with refcodes EDEVAK [106] and NUVSEC [107] (Schemes 18 and 19) and some co-crystal compounds (for example BARHMP [108] and VAFRIE [109], see Schemes 20 and 21) were reported. 1 There is the hydrogen-bonded amide molecule in the structure, i.e.…”