Rhodium phenylphosphine

Use of the same benzyl(methyl)phenylphosphine and DIOP rhodium(I) catalysts with ,/3-unsaturated carbonyls has led to some interesting selectivity patterns (297, 298). Dihydrosilanes undergo 1,2-addition at the carbonyl of substrates such as 2-methylcyclohexenone, mesityl oxide,... 

Hayashi proved the validity of this catalytic cycle by the observation of aU three intermediates and their respective transformations using NMR experiments (Scheme 3.5) [16]. Transmetallation of a phenyl group from boron to rhodium takes place by addi-hon of phenylboronic acid 2 m to hydroxo-rhodium complex 16 in the presence of tri-phenylphosphine to generate the phenylrhodium complex 17. The reaction of 17 with 2-cyclohexenone la gives oxa- j-allylrhodium 18, which is converted immediately into hydroxo-rhodium complex 16 upon addition of water, liberating the phenylation product 3 am. In this NMR study, triphenylphosphine was used to stabilize the phenylrho-dium(I) complex. In the absence of triphenylphosphine, the characterization of the phenyl-rhodium species was unsuccessful. 

C46H4g02P2Rh2S2, Rhodium, dicarbonylbis(tri-phenylphosphine) bis(/i-2-methylpropa-nethiolato)di-, 34 123... 

When rhodium is used, this ring effect is very important only with trans-propenylbenzene, and it becomes even more important when tri-phenylphosphine is added to rhodium. 

The Influence of Potentially Bridging Groups in Homogeneous Hydrogenation with Rhodium Complexes A Study of para-Dimethylamino-Substituted Phenylphosphine Metal Complexes... 

Sodium triacetoxyborohydride, 283 Titanium(III) chloride, 302 Tributyltin hydride, 316 Zinc borohydride, 167 of alkenes to alkanes (R)-(-F)- and (S)-(-)-2,2 -Bis(di-phenylphosphine)-l,1 -binaphthyl, 36 [1,4-Bis(diphenylphosphine)-butanej(cycloheptatriene)-rhodium(I) tetrafluoroborate, 89 [ 1,4-Bis(diphenylphosphine)butane]-(norbornadiene)rhodium(I) tetrafluoroborate, 37... 

P-31 NMR was a powerful tool in studies correlating the structure of tertiary-phosphine-rhodium chloride complexes with their behavior as olefin hydrogenation catalysts. Triphenylphosphine-rhodium complex hydrogenation catalyst species (1) were studied by Tolman et al. at du Pont and Company (2). They found that tris(triphenylphosphine)rhodium(I) chloride (A) dissociates to tri-phenylphosphine and a highly reactive intermediate (B). The latter is dimerized to tetrakis(triphenylphosphine)dirhodium(I) dichloride (C). 

Since there were no known definitive studies of the crucial equilibria between the tris-(triphenylphosphine)- and bis-(tri-phenylphosphine)rhodium(I) carbonyl hydride complexes, it was decided to study such equilibria by P-31 NMR spectroscopy. The... 

P-31 NMR studies also were carried out in a similar manner on rhodium complexes of two chelating bisphosphines—bis-l,3-diphenyl-phosphinopropane and bis-l,2-diphenylphosphinoethane. These complexes were generated in solution via ligand displacement from tris(tri-phenylphosphine)rhodium carbonyl hydride. For example, one of the possible displacement products of bis-l,3-diphenylphosphinopropane (F) is a cis-chelate (G) that can undergo dissociation to yield a chelating bisphosphine complex (H) ... 

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-... 

Reduction of the amide (123 R1 = R2 = OMe) with sodium aluminium hydride gave a mixture of the bases (125 R1 = R2 = OMe), (127), and (130),165 and the last of these lost carbon monoxide when heated with tris(tri-phenylphosphine)rhodium chloride in benzene to give the dimethyl ketal of 14/3-methylcodeinone, which could be hydrolysed to 14j8-methylcodeinone, the 7,8-dihydro-derivative of which proved to be identical with material previously prepared by a different route (see Volume 9, p. 116). The corresponding morphinone and dihydromorphinone have been prepared.164... 

Acetic acid (1.0 mL) is added to a suspension of hydridotetrakis(tri-phenylphosphine)rhodium (0.58 g) in ethanol (15.0 mL), and the mixture is heated under reflux for 15 min. During this time the starting material dissolves and orange crystals are deposited. The mixture is cooled the crystals are filtered off, washed successively in methanol (2 x 10 mL), water (2 x 10 mL), and methanol (2 x 10 mL), then dried in vacuo. 

Bis(3-diphenylphosphinopropyl)phenylphosphine (99) forms chloro, bromo and iodo rhodium(I) complexes (equations 253 and 254). The bromo complex can be obtained by addition of a large excess of LiBr to [RhCl(cod)]2 prior to addition of the neutral ligand.1051 The iodo complex has also been prepared from [RhI(CgH12)]2.1051,1052 The halo complexes (100) have been shown to be square planar by X-ray crystallography.1051... 

B2N4P4Rh2Cii8H,2o, Rhodium(I), tetrakis(l-isocyanobutane)bis[methylenebis(di-phenylphosphine)]di-, bis[tetrapheny 1-borate(l — )], 21 49... 

PRhC32H38, Rhodium, (l,4-butanediyi)(Ti -pentamethylcyclopentadienyI)(tri-phenylphosphine)-, 22 173 PS2C4H11, Phosphinodithioic acid, diethyl-molybdenum complexes, 23 120, 121 PS3C,2H27, Phosphorotrithious acid tributyl ester, 22 131... 

P2PtC3BH34, Platinum(O), (ethene)bis(tri-phenylphosphine)-, 24 216 P2RhCiiH23, Rhodium(I), (n -cyclopenta-dienyl)bis(trimethylphosphine)-, 25 159 P2RUC49H40, Ruthenium(II), (i) -cycIopenta-dienyl)(phenylethyyl)bis(triphenyl-phosphine)-, 21 82... 

SOOsP2C4,H44, Osmium, carbonyl(5-thioxo-1,3-pentadiene-1,5-diyl-C, C, 5)bis(tri-phenylphosphine)-, 26 188 SO2C7H, Benzenesulfonic acid, 4-methyl-, rhodium complex, 27 292 S04PC,H,2. 2-Butenedioic acid, 2-(dimeth-ylphosphinothioyl)-, dimethyl ester, manganese complex, 26 163 SO C H , Thiophenetetracarboxylic add. tctramethyl ester, 26 166... 

RhPC32Hn, Rhodium, (1,4-butanediyl)(-q5-pen-tamethylcyclopentadienyl)(tri-phenylphosphine)-, 22 173 Rh2B2N4P4CMIHl2o, Rhodium(I), tetrakis(l-iso-cyanobutane)bis[methylene(di-phenylphosphine)]di-, bis[tetra-phenylborate(l -)], 21 49 Rh20 C,6Hw, Rhodium(l), bis(-q4-1,5-cycloocta-diene)-di-p.-hydroxo-di-, 23 129 IUitO iiHm, Rhodium(l), bis(i)4-l, 5-cydoocta-diene)-di-p.-methoxy-di-, 23 127 RhiOJ K, Rhodium(I), dicarbonylbis-(p-2-methyl-2-propanethiolato)-bis(trimethyl phosphite)di-, 23 124 Rh2Ol2P4S2HM, Rhodium(I), bis(p.-2-methyl-2-propanethiolato)-tetrakis(trimethyl phos-phite)di-, 23 123... 

As far as is known, the only industrial application of the water-soluble catalyst for the hydroformylation of 5 -functionalized alkenes has been developed by Kura-ray [17]. In this process, 7-octen-l-al is hydroformylated into nonane-1,9-dial, a precursor of nonene-l,9-diol, by using a rhodium catalyst and the monosulfonated tri-phenylphosphine as water-soluble ligand in a 1 1 sulfolane/water system. At the completion of reaction, the aldehydes are extracted from the reaction mixture with a primary alcohol or a mixture of primary alcohol and saturated aliphatic hydrocarbon (cf. Section 6.9). 

ClPjRhC54H45, Rhodium(l), chlorotris(tri-phenylphosphine)-, 28 77 ClP4RhS2C4jH54, Rhodium, chloro[[2-[(diphenylphosino)methyl]-2-methyl-... 

ClPjRhCjjHjo, Rhodium(I), chloro(Ti -f rfl/i /ro-tetraphosphorus)bis(tri-phenylphosphine)-, 27 222 ClRhC (H2g, Rhodium(I), chlorobis(cyclo-octene)-, 28 90... 

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