Bisphosphine ligands containing two o-N,N-dimethylanilinyl substituents at each phosphorus atom

Abstract

The synthesis and complete characterization of the family of tetra(amine)bisphosphine ligands (oNMe 2 C 6 H 4 ) 2 P-(X)-P(o-NMe 2 C 6 H 4 ) 2 , where X = CH 2 (dmapm), (CH 2 ) 2 (dmape), and CH(CH 2 ) 3 CH (dmapcp), are described. Crystal structure data are compared with known, analogous bisphosphines containing o-pyridyl or phenyl substituents in place of the o-dimethylanilinyl groups. Several short, intramolecular C-H···N distances in the anilinyl derivatives may represent the presence of weak hydrogen bonds.Résumé : On décrit la synthèse et la caractérisation complète d'une famille de ligands tétra(amine)bisphosphine, (o-NMe 2 C 6 H 4 ) 2 P-(X)-P(o-NMe 2 C 6 H 4 ) 2 , dans lesquels X = CH 2 (dmapm), (CH 2 ) 2 (dmape) et CH(CH 2 ) 3 CH (dmapcp). On a comparé leurs structures cristallines à celles de bisphosphines connues, analogues, contenant des substituants o-pyridyle ou phényle à la place des groupes o-diméthylanilinyles. Plusieurs distances intramoléculaires C-H···N dans les dérivés anilinyles sont courtes et elles peuvent être le reflet de la présence de faibles liaisons hydrogènes.

A Potentially Limitless Chiral Pool via Conglomerate Crystallisation: Unidentified Spontaneous Resolution in the CSD.

“…This highlights the possibility of utilizing conglomerate crystallisation as a new chiral pool. Within this list are C2 symmetrical pyrimidine (OBIPAR [76] ), phosphine (LUSZOO [77] ) and imidazole (ROJPOW [78] ) ligands, an atropsiomeric quinoline (TUWFAT [79] ), an α-methylpyridine (DOBWUN [80] ), and a chiral salen ligand (TUNMOF [81] ). Potential types of organocatalysts such as the C2 symmetrical diol (NULZEA [82] ), a PTC (phase transfer catalyst) crown ether (NOCNIC [83] ), and chiral phosphoric acid (CUVGAB [84] ), chiral ureas (RIPBUN, [85] AZUDAB [86] ), benzotetramisole (YAMBAS [87] ), amino-alcohol (HARFEN [88] ), and imidazole (PURJUJ [89] ) may also find use in asymmetric synthesis.…”

Homo- and Heterobimetallic Precursor Catalysts for the Heck Reaction, and a Proposal for a General Catalytic Cooperativity Index

“…1,1-Bis[di(o-N,N-dimethylanilinyl)phosphino]-methane (dmapm), [23] diphenylphosphino-N,N-dimethylaniline (PMA), [24] MCl 2 (PMA) (M Pt, Pd) [24] and transPdCl 2 (PhCN) 2 [57] were made according to literature procedures. The synthesis and coordination chemistry of monometallic Pt and Pd complexes of dmapm [34] will be published elsewhere.…”

“…The strong tendency for -CH 2 -tethered bisphosphines to bridge metal centres, [22] combined with the possibility of five-membered P,N-chelate ring formation, made us realise that the ligand 1,1-bis[di(o-N,N-dimethylanilinyl)phosphino]methane (dmapm) [23] would give access to homo-and heterobimetallic Group 10 complexes of the general form illustrated in Figure 1. Use of these complexes as Heck catalysts allows, in principle, for the assessment of the catalytic effects of a second metal centre, not supplied simply as a separate additive, but as an integral component of a bimetallic catalyst that puts two metal centres in close juxtaposition.…”

Small bite angle diphosphines: synthesis of Ph(p-tolyl)PCH2PPh(p-tolyl) upon lithium reduction of Ph2P(p-tolyl)—molecular structure of anti-[Mo(CO)4{Ph(p-tolyl)PCH2PPh(p-tolyl)}]

“…2) [6]. A number of other compounds of the type Ar 2 PCH 2 PAr 2 have also been prepared [7][8][9][10][11][12][13][14]. Recent research in our group has concerned the synthesis of new small bite angle diphosphines based on the dppm framework.…”