Phosphine complexes with silver

In the presence of air, trimethyl, triethyl, and tributylphosphine combust spontaneously. In the presence of pure oxygen, even though it was at a low temperature, triethylphosphine detonated. In the same conditions, triphenyl-phosphine does not seem to be dangerous. Trimethylphosphine can be stored safely in the air in the form of a complex with silver iodide. 

In extension of this work, a platinum complex with a chiral phosphine ligand and a BINOL template was employed as a metallomonomer [28]. After removal of the template and activation of the complex with silver salts (generation of Lewis acidic platinum centers) the MIP was used as a catalyst for an asymmetric ene reaction. Enantioselectivities of 72% ee were observed (Fig. 15). This compares well to... 

The inability of the tri(2-cyanoethyl)phosphine to form 3 1 complexes with silver may be due to its bulk. Therefore, several other tertiary phosphines were also titrated and the titration curves are shown in Fig. 8. It can be seen that the two derivatives with large substituents (2 and 5, 2-cyanoethyl- and cyclohexyl-) only form stable 2 1 complexes. The butyl and phenyl derivatives (3 and 4) form 3 1 complexes as well as the 2 1. All form... 

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

B. (2000) Gold and Silver Complexes with the Ferrocenyl Phosphine FcCH2PPh2 [Fc = (Tl5-C5H5)Fe(h5-C5H4)]. Inorganic Chemistry, 39(4), 680-687. 

An extension of the research on silver complexes with Lewis base-functionalized mono(A-heterocyclic carbene) ligands has been made toward the better-studied and stronger coordinating phosphine systems. The reaction of a diphenylphosphine-functionalized imidazolium salt with silver oxide in dichloromethane affords a trinuclear silver carbene complex 50, as confirmed by electrospray-ionization mass spectrometry.96,97 Metathesis reaction of 50 in methanol using silver nitrate gives 51 in 33% yield. The crystal structures of 51 were found to be different when different solvents were used during crystallization (Scheme 12).97 One NO3- anion was found to be chelated to... 

Method B2 A modification of method B4 for the preparation of catalysts starting from organonickel halides consists in the exchange of the halide anion by an anion of a strong complex acid, HY. This has been accomplished by reacting 7r-allylnickel halides (1) or their phosphine adducts (2) with silver salts (65) ... 

Catalytic forms of copper, mercury and silver acetylides, supported on alumina, carbon or silica and used for polymerisation of alkanes, are relatively stable [3], In contact with acetylene, silver and mercury salts will also give explosive acetylides, the mercury derivatives being complex [4], Many of the metal acetylides react violently with oxidants. Impact sensitivities of the dry copper derivatives of acetylene, buten-3-yne and l,3-hexadien-5-yne were determined as 2.4, 2.4 and 4.0 kg m, respectively. The copper derivative of a polyacetylene mixture generated by low-temperature polymerisation of acetylene detonated under 1.2 kg m impact. Sensitivities were much lower for the moist compounds [5], Explosive copper and silver derivatives give non-explosive complexes with trimethyl-, tributyl- or triphenyl-phosphine [6], Formation of silver acetylide on silver-containing solders needs higher acetylene and ammonia concentrations than for formation of copper acetylide. Acetylides are always formed on brass and copper or on silver-containing solders in an atmosphere of acetylene derived from calcium carbide (and which contains traces of phosphine). Silver acetylide is a more efficient explosion initiator than copper acetylide [7],... 

Silver(I) halide complexes of oA could not be prepared. The phosphine ap, however, reacts with silver iodide to give a colourless, unstable, non-conducting compound of empirical formula Agl(ap). This compound reacts with excess ap to give the stable 2 1 adduct Agl(ap)2- Silver bromide and silver chloride react directly with the ligand to give similar 2 1 adducts. These complexes are essentially monomeric, contain three-coordinate silver (I) and uncoordinated olefinic groups. The structure of the 1 1 adduct is unknown. 

Finally, binuclear lanthanide(III)-silver(I) shift reagents are noteworthy. These form complexes with olefins, aromatic rings, halogenated saturated hydrocarbons, and phosphines. Due to the lack of polar groups, these functionalities do not give significant LIS with common mononuclear LSR. Applications of this binuclear technique have been reviewed261 for example, the Z- and E-isomers of 2-octene can be differentiated. 

From the bond distances in Table 28,188-192 it can be seen that the Ag—P distances remain relatively constant, whilst the Ag—X distance varies depending on the halide. This was also the case with 1 2 silver complexes with monodentate phosphines. 

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