Phosphines ethylene derivatives

T ris( diethy lamino)phosphine Ethylene derivs. by twofold extrusion... 

Tri-n-butyltin hydridelbis(dibenzylideneacetone) palladium (O)ltri (2-fury I) phosphine <-Ethylene derivs. from enol triflates C = C(OTf) C = CH... 

Triphenyl phosphine Ethylene derivatives and a-bromoalkylidenephosphoranes from 1,2-dibromides... 

Bochwic, B., and Michalski, J., Eormation of C-P bonds by addition of di-alkyl hydrogen phosphonates and alkyl hydrogen phosphinates to activated ethylenic derivatives. Nature, 167, 1035, 1951. 

Bochwic, B., and Michalski, J., Organic phosphorus compounds. Part 1. Addition of dialkyl hydrogen phosphonates to ethylenic derivatives, Rocz. Chem., 25, 338, 1951 Chem. Abstr, 48, 12013a, 1954. Issleib, K., and Vollmer, R., o-Substituted benzenephosphonic acid diethyl ester and t)-amrno, o-hydroxy, and o-mercaptophcnyl phosphine, Z. Chem., 18, 451, 1978. 

Ethylene derivatives from phosphinic acid esters... 

Phosphine-substituted derivatives of ethylene are known in syn and anti forms. In this case the two isomers can be prepared by the action of LiPPh2 on the appropriate ethylene derivative. 

Cyclic phosphinic from phosphonous acid derivs. and ethylene derivs. 

Hydroformylation of PhCH=CHMe in the presence of RhCl(PPh3)3 produces PhCH(CHO)-CHa-CH3 and PhCH3-CH(CHO)-CH3, as well as some PhCH2 CH2 CH3. Both Rh4(CO)i2 and mixed carbonyl-phosphine complexes derived from Rh4(CO)i2 and from Rh,(CO)ie are active catalysts for hydroformylation of alkenes. Acyl-rhodium intermediates may be important when Rh4(COX2 is the catalyst, for [Rh-(C0)2(02CR)]2 dimers have been isolated from alkene hydroformylations in which this polynuclear carbonyl has been the catalyst. Rh4(CO)i2 also catalyses the reaction between ethylene and carbon monoxide, which produces several products, including octane-3,6-dione, undecane-3,6,9-trione, and tetradecane-3,6,9,12-tetraone. The products obtained indicate a mechanism in which addition of ethylene to rhodium and insertion of carbon monoxide into a rhodium-carbon bond alternate. ... 

Synthesis of ethylene derivatives from 0x0 compounds and phosphonic acid esters or phosphine oxides... 

The ruthenium analogue of 47 Ru(ri5-C5Ph5)(CO)2Br (48) is also available, when Fe(CO)5 is replaced by Ru3(CO)12 [68]. A wide range of substitution products were obtained through replacement of both carbonyl and bromide ligand against two-electron ligands L such as phosphines, phosphites, and ethylene. Electrochemistry of these derivatives were studied in some detail. 

Sugar derivatives of phosphanes can be made by reaction of ethylene glycol derivatives with sugar diacetonides to form monoallyl ethers, which can be brominated at the double bond. These compounds react with phenyl-and diphenylphosphanes to yield ligands with a sugar function in the side chain (57). Phosphinated glucopyranosides were prepared by Oehme and... 

Fumigant -calcium cyanide as [CYANIDES] (Vol 7) -ethylene oxide as [ETHYLENE OXIDE] (Vol 9) -methyl bromide as [BROMINE COMPOUNDS] (Vol 4) -phosphine as [PHOSPHINE AND ITS DERIVATIVES] (Vol 18)... 

Hydroformylation - [CARBON MONOXIDE] (Vol 5) - [OXO PROCESS] (Vol 17) -of allyl alcohol [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) -catalysts for [CATALYSIS] (Vol 5) -C-19 dicarboxylic acids from [DICARBOXYLIC ACIDS] (Vol 8) -of ethylene [ETHYLENE] (Vol 9) -of ethylene [PROPYL ALCOHOLS - N-PROPYLALCOLHOL] (Vol 20) -of maleate and fumarate esters [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -phosphine catalyst [PHOSPHORUS COMPOUNDS] (Vol 18) -platinum-group metal catalysts for [PLATINUM-GROUP METALS] (Vol 19) -rhodium catalysis [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -ruthenium cmpds or catalyst [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -use of coordination compounds [COORDINATION COMPOUNDS] (Vol 7)... 

Our attempts to fully characterize these clusters have been hampered by their relatively low solubility, poor crystallinity (we have been unable to grow crystallographic quality crystals) and high reactivity. In order to prepare derivatives with better solubility characteristics, we have allowed several small molecules to react with the blue Mo6-cluster. Ethylene reacts to give a violet adduct, H2 and CO black ones, and phosphites and phosphines give several products, depending on stoichiometry. None of these derivatives are as yet fully characterized. 

The electron-releasing phosphine promotes oxidative addition of the bromo derivative to Pd(0) and, because of its bulkiness, readily generates free coordination sites by dissociation. Ethylene coordination and insertion then occur, followed by reductive elimination, triethylamine acting as a base to neutralize hydrogen bromide. As in most cases of transition metal-catalyzed reactions the fine details of the mechanism are still under investigation. Thus recent studies by Amatore s group suggest that the palladium(O) species formed by reduction of palladium acetate is an anionic acetato complex. 

---