Tris- phosphine carbonyls

Very recently, the benzannulation has been applied to chromium(phosphine)carbonyl complex 34, which is suited for subsequent immobilization by sol-gel methodology the tri-... 

Primary Amyl Alcohols. Primary amyl alcohols (qv) are manufactured by hydroformylation of mixed butenes, followed by dehydrogenation (114). Both 1-butene and 2-butene yield the same product though in slightly different ratios depending on the catalyst and conditions. Some catalyst and conditions produce the alcohols in a single step. By modifying the catalyst, typically a cobalt carbonyl, with phosphoms derivatives, such as tri( -butyl)phosphine, the linear alcohol can be the principal product from 1-butene. 

Bis-[triphenylphosphin]-carbonyl-organo-rhodium(0) bzw. -iridium(O) sind aus den entsprechenden Dichloro-Komplexen bzw. Carbonyl-tris-[triphenyl-phosphin]-rhodium(0) bzw.-iridium(O) aus den Chloro-Komplexen zuganglich7 ... 

Pyrophoric carbonyl metals Phosphine Tri butyl phosphine ... 

With tertiary phosphines, phosphites and iso-nitriles, the substitution of the carbonyl groups in Co4(CO)i2 and Rh4(CO)i2 occurs very easily up to the tri-substituted complex. It is sufficient to add slowly at room temperature a solution of the ligand to a solution of the dodecacarbonyl ... 

Cyclododecene may be prepared from 1,5,9-cyclododecatriene by the catalytic reduction with Raney nickel and hydrogen diluted with nitrogen, with nickel sulfide on alumina, with cobalt, iron, or nickel in the presence of thiophene, with palladium on charcoal, with palladimn chloride in the presence of water, with palladium on barium sulfate, with cobalt acetate in the presence of cobalt carbonyl, and with cobalt carbonyl and tri- -butyl phosphine. It may also be obtained from the triene by reduction with lithium and ethylamine, by disproportionation, - by epoxidation followed by isomerization to a ketone and WoliT-Kishner reduction, and from cyclododecanone by the reaction of its hydrazone with sodium hydride. ... 

In the case of phosphine, especially tri-n-butyl and triphenyl phosphines, an active phosphine complex is formed in the reaction medium via reaction with nickel carbonyl. This complex is a very active species provided that the optimum concentration of phosphine is used. Low phosphine concentration results in a loss of the effective nickel concentration through the formation of nickel tetra-carbonyl, nickel metal or nickel iodide. The absolute concentration of phosphine is less important than the P/Ni ratio. In addition to form the stable Ni-P catalyst, the phosphine has to compete with other ligands in the reaction mixture for nickel. With high carbon monoxide partial pressure, there is more CO in solution to compete with phosphine favoring the formation of the carbonyl, which is inactive under the reaction conditions. Hence with high carbon mon-... 

Fe2Cu2N402P4C8gHi42, Copper, bis carbonyl-(cyclopentadienyl)irondi(/i-cyano)bis(tri-cyclohexylphosphine)-, 34 175 Fe2Cu2N402P4CiooH94, Copper, bis carbonyl-(cyclopentadienyl)irondi(/4-cyano)-bis(tri(para-tolyl)phosphine)-, 34 176 Fe2Cu2Ng02C24H22, Copper,... 

Cu2Fe2N4P4CiooH94, Copper, bis carbonyl-(cyclopentadienyl)irondi(/i-cyano)-bis(tri(pcira-tolyl)phosphine)-, 34 176... 

D. CARBONYL(THIOCARBONYL)TRIS(TRIPHENYL-PHOSPHINE)OSMIUM(O)6... 

TRI- AND TETRANUCLEAR CARBONYL-RUTHENIUM CLUSTER COMPLEXES CONTAINING ISOCYANIDE, TERTIARY PHOSPHINE, AND PHOSPHITE LIGANDS. RADICAL ION-INITIATED SUBSTITUTION OF METAL CLUSTER CARBONYL COMPLEXES UNDER MILD CONDITIONS... 

The formation of both 12 and 13 during the reduction of 4 in the presence of triphenylphosphine indicated not only that one-half of an equivalent of the added phosphine was taken up, but also that the intermediate formed is the bisphosphine complex, (< 3P) JRhCl, proposed as the reactive intermediate in hydrogenation runs using 1 as the catalyst (1). This assumption is further supported by the fact that the product stereochemistry (cis/trans = 2.0) and lack of double bond isomerization observed on hydrogenation of 7 with this reaction mixture corresponds directly with the data obtained on hydrogenation of 7 using pre-hydro-genated 1 (3). When the reduction of 4 was repeated in the presence of tri-p-tolyphosphine, the carbonyl complex formed was isolated and shown by PMR spectroscopy to contain 1.5 equivalents of triphenylphosphine and 0.5 equivalent of the tri-p-tolyphosphine, as expected. 

For cis-chelate complexes of rhodium and bisphosphines as catalysts, indeed relatively low ratios of n/i aldehyde products were reported (12, 13). Using a 1 1 mixture of H CO at atmospheric pressure, Sanger reported n/i ratios ranging from 3 to 4 for propylene hydroformylation (12). However, his catalyst systems were produced by adding less than 2 mol of bisphosphine per mole tris(triphenyl-phosphine)rhodium carbonyl hydride. When an excess of the chelating bisphosphines was used by Pittman and Hirao (13), low n/i ratios close to 1 were produced from 1-pentene using a mixture of H2/CO at 100-800 psi between 60° and 120°C. 

As shown by the data of Table I, adding increasing amounts of the three phosphines used in the present studies to tris(tri-phenylphosphine)rhodium(I) carbonyl hydride produces catalyst systems of reduced activity as indicated by the reduced reaction rate. As expected, an increasing excess of triphenylphosphine results in an increased 1-butene hydroformylation selectivity towards the n-... 

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