Containers phosphine

The following nitrogen containing phosphinic acid derivatives have been proposed as chelating and wetting agents [184]. They were prepared from chloromethylphosphinic acid with the appropriate amines see Eq. (Ill) ... 

Scheme 1.12 Test reaction with (5)-proline-derived sulfur-containing phosphine ligands.

V-phosphino snlfoximine ligands, BlNOL-derived 250-2 silylcyanations 327-8 snlfur-containing phosphine ligands 17-18... 

Many catalysts, both immobilized (on solid state supports) and heterogeneous, contain phosphines and other phosphorus compounds, so that solid state NMR has become an invaluable tool in the study of catalysis. 

Figure 29 rr-Conjugated organoboron polymer containing phosphine ligands with Ru (41), Pt (42a), or Pd (42b) in the polymer backbone. (Adapted from refs. 62 and 63.)... 

Indium and gallium coordination compounds containing phosphine ligands have recently aroused interest for their widespread application as intermediates in the preparation of the Group 13 - Group 14 semiconductors [4], Since the early reports about compounds with transition metal-indium bonds [51, relatively little research has been reported in this field. However there is a growing interest in the coordination chemistry and structural features of heterometallic indium [6] and gallium complexes [7] which are also attractive as potential precursors of new materials with particular properties. 

In addition to direct DuPhos and BPE analogues, several other ligands containing five-membered phosphacycles have been reported (Fig. 24.6). As early as 1991, non-C2-symme trie phospholane-containing phosphines 37-39 were reported by Brunner and Limmer [7]. These were prepared by base-induced addition of the secondary phospholane to the appropriate diphenylphosphino-substi-tuted olefin. As for the symmetrical 3,4-disubstituted bisphospholanes, enantios-electivities for the Rh-catalyzed reduction of a-acetamidocinnamate were poor. 

Another series of achiral iridium catalysts containing phosphine and heterocyclic carbenes have also been tested in the hydrogenation of unfunctionalized alkenes [38]. These showed similar activity to the Crabtree catalyst, with one analogue giving improved conversion in the hydrogenation of 11. 

Using the Multipin method, Gilbertson then synthesized 27 undecapeptides on solid phase, which were presumed to have a helical conformation. This was induced by frequent use of the a-alkylated amino acid aminoisobutyric acid. The phosphine-thiooxide-containing residues were positioned in the i and i + 4 positions, which would lead to the two phosphines being adjacent in the helical peptide chain. In addition, Gilbertson synthesized 36 peptides containing phosphines in the i and i + 1 positions. 

These polymers show lower water uptake than the analogous sulfonated poly(arylene ether sulfone) materials, possibly suggesting some interaction between the aromatic nitrile and sulfonic acid. The phosphine oxide functional moiety could also be used as a compatibilizer with other materials. Sulfonated poly(arylene ether phosphine oxide sulfone) terpoly-mers have been prepared both with sulfonated triphenyl phosphine oxide and with triphenyl phosphine oxide with 3,3 -disulfonate-4,4 —dichlorodiphenyl sulfone as the sulfonic acid bearing monomer. Block copolymers containing phosphine oxide appear to avoid the ether—ether interchange that results when non—phosphine oxide blocks are utilized, and this is being further pursued. ... 

Figure 24. Synthesis of a five-membered ring sulfonated polyimide containing phosphine oxide.

Figure 7. Nitrogen-containing phosphine ligands (continued)...

The two N-containing phosphines, N3P 206 [179] and PAA-pyrphos 207 [180] served as useful components of hydroformylation and hydrogenation catalysts. 

Scheme 7.4 Formation of surface rhodium siloxide complexes containing phosphine and hydride ligands.

In many cases, the driving force behind studies of Ru or Os complexes containing phosphine ligands incorporating O-donors is potential application in catalysis. A common feature of many of the P,0-bound ligands described in this section is their partial lability, with the conversion of a P,0- to P-coordinated ligand as another Lewis base such as CO or RNC displaces the O-donor. 

Fig. 14. Schematic representation of four types water-soluble PAMAM dendrimers containing phosphine ligands.

Le Gendre and Moise [50] produced an allenylidene ruthenium complex analogous to I but with a titanium(IV)-containing phosphine such as XI (Scheme 8.9). Its rearrangement into indenylidene was not observed and its catalyst activity remained moderate. 

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