Phosphine, trimethyl metal complexes

Phosphine, seleno-metal complexes, 664 bidentate, 664 Phosphine, tributyl-, 992 Phosphine, trichloro-, 990 Phosphine, tricyclohexyl-, 992 Phosphine, triethyl-, 992 Phosphine, trifluoro-jt acidity, 1034 Phosphine, triisopropyl-, 992 Phosphine, trimethyl-, 990, 992 oxides... 

The use of a lipophilic zinc(II) macrocycle complex, 1-hexadecyl-1,4,7,10-tetraazacyclododecane, to catalyze hydrolysis of lipophilic esters, both phosphate and carboxy (425), links this Section to the previous Section. Here, and in studies of the catalysis of hydrolysis of 4-nitrophenyl acetate by the Zn2+ and Co2+ complexes of tris(4,5-di-n-propyl-2 -imidazolyl)phosphine (426) and of a phosphate triester, a phos-phonate diester, and O-isopropyl methylfluorophosphonate (Sarin) by [Cu(A(A(A/,-trimethyl-A/,-tetradecylethylenediamine)l (427), various micellar effects have been brought into play. Catalysis of carboxylic ester hydrolysis is more effectively catalyzed by A"-methylimidazole-functionalized gold nanoparticles than by micellar catalysis (428). Other reports on mechanisms of metal-assisted carboxy ester hydrolyses deal with copper(II) (429), zinc(II) (430,431), and palladium(II) (432). 

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],... 

Green et al. observed that the tantalum complex 101 is converted into the bicyclic complex 109 after prolonged exposure to sodium and trimethyl-phosphine.930 Two phosphine ligands of 101 are easily displaced by butadiene, affording the complex 110, while treatment of 109 with dihydrogen leads to the reduction of the metallic center. In both cases, the metallacycle remains intact.930... 

M. J. Wax, J. M. Stryker, J. M. Buchanan, C. A. Kovac, and R. G. Bergman, Reversible C—H Insertion/Reductive Elimination in ( 5-Pentamethylcyclopentadienyl)(trimethyl-phosphine)iridium Complexes. Use in Determining Relative Metal-Carbon Bond Energies and Thermally Activating Methane, J. Am. Chem. Soc. 106, 1121-1122 (1984). 

The insoluble alkynylsilver complexes are regarded as coordination polymers (RC=CAg)co with cross-linking between the metal atoms and the ethynyls of adjacent RC=CAg units. Donor molecules (L) such as tertiary amines, phosphines and arsines can partly break down the polymeric structure. Thus the reactions of PhC=CAg with isopropylamine, trimethyl-, triethyl- or triphenylphosphine and triethylarsine yield the 1 1 complexes of the composition [(L)AgC=CR]49-51. 

The hydrogen-bond acceptor properties of a strain phosphine molecule (3), and its deprotonated derivatives (4), (5), and (6) have been examined at the MP2/6-311- -- -G(d,p) level of theory. In addition, complexation of these with metallic atoms, i.e, the anion (4) with Li" ", dianion (5) with Be " ", and the trianion (6) with B + (in order to obtain neutral complexes) has been considered, and the effects of such complexation in their hydrogen-bonding characteristics were analyzed. The results obtained for the complexes were compared with the analogous ones of trimethyl-phosphine oxide. It was shown that the strain decreases the... 

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