14653-50-0

Upstream product

• 14694-95-2 Wilkinson's catalyst 
• 274-07-7 benzo[1,3,2]dioxaborole 
• 15318-33-9 trans-carbonyl(chloro)bis(triphenylphosphine)rhodium(I) 
• 1095062-41-1 [RhCl(Ph₃P)2] 
• 603-35-0 triphenylphosphine 
• 15318-33-9 chlorocarbonylbis(triphenylphosphine)rhodium(I) 
• 16973-49-2 hydridotris(triphenylphosphine)rhodium 
• 58-89-9 LINDANE 
• 41823-72-7 bis[bis(trimethylsilyl)methyl]tin(II) 
• 100-42-5 styrene 
• 69547-87-1 [RhHCl(2-benzylideneamino-3-methylpyridine^(1-))(PPh₃)2] 
• 1562376-71-9 trans-[rhodium(I)chloride(triphenylphosphine)2(propanoyl-(5,5′,6,6′-tetramethyl-3,3′-di-tertbutyl-1,1′-biphenyl-2,2′-diyl)phosphite)] 
• 1562376-72-0 trans-[rhodium(I)chloride(triphenylphosphine)2(propanoyl-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite)] 
• 1562376-73-1 trans-[rhodium(I)chloride(triphenylphosphine)2(phenylacetyl-(5,5′,6,6′-tetramethyl-3,3′-di-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite)] 

Downstream Products

• 15318-33-9 trans-carbonyl(chloro)bis(triphenylphosphine)rhodium(I) 
• 33308-64-4 dicarbonylcyclopentadienyl(p-methoxyphenyl)iron 
• 59349-68-7 {RhCl(CS)(PPh₃)2} 
• 186790-68-1 [RhCl(BO₂C₆H₃CH₃)2(P(C₆H₅)3)2] 
• 201733-47-3 [RhCl(BO₂C₆H₃CH₃)2(P(C₆H₅)3)2] 
• 201733-52-0 [RhCl(BS₂C₆H₃CH₃)2(P(C₆H₅)3)2] 
• 201733-50-8 [RhCl(BO₂C₆H₃OCH₃)2(P(C₆H₅)3)2] 
• 201733-38-2 [RhCl(BO₂C₆H₄)2(P(CH₃)2(C₆H₅))3] 
• 144436-50-0 [(Ph₃P)2RhCl(phenylene-1,2-dioxyboryl)2] 

Relevant academic research and scientific papers

Convenient synthesis and molecular structure of the cyclometallated complex [IrCl(H)(C6H4PPh2)(PPh3)2]

Dedicated to Professor Hubert Schmidbaur on the occasion of his 80th birthday The reaction of [{Ir(μ-Cl)(coe)2}2] (coe=cis-cyclooctene) with triphenylphosphane (molar ratio of Ir to P=1 : 3) in dichloromethane at room temperature afforded after a short reaction time the cyclometallated complex [IrCl(H)(C6H4PPh2)(PPh3)2] (1) in almost quantitative yield. The molecular structure of the title compound 1 was determined by an X-ray diffraction study.

A mechanistic description of unexpected room temperature C-H and P-C bond activation by wilkinson's catalyst

The Wilkinson's catalyst, (PPh3)3RhCl dissolved in benzene under nitrogen or under high vacuum undergoes a series of unreported reactions at room temperature. The preliminary mechanistic description involves a series of consecutive intramolecular and intermolecular phosphine exchanges, benzene oxidative addition, and biphenyl reductive elimination.

Mixed anhydride complexes of rhodium(i) and ruthenium(ii)-their synthesis and ligand rearrangements

The coordination chemistry and solution behaviour of Rh(i) and Ru(ii) complexes derived from mixed anhydride ligands of carboxylic acids and phosphorus acids were explored. Similar to the free ligand systems, mixed anhydride complexes rearranged in solution via a number of pathways, with the pathway of choice dependent on the mixed anhydride employed, the auxiliary ligands present as well as the nature of the metal centre. Plausible mechanisms for some of the routes of rearrangement and by-product formation are proposed. Where stability allowed, new complexes were fully characterised, including solid state structures for four of the unrearranged mixed anhydride complexes and two of the interesting rearrangement products.

Coordination and organometallic chemistry of relevance to the rhodium-based catalyst for ethylene hydroamination

The RhCl3·3H2O/PPh3/nBu 4PI catalytic system for the hydroamination of ethylene by aniline is shown to be thermally stable by a recycle experiment and by a kinetic profile study. The hypothesis of the reduction under catalytic conditions to a Rh I species is supported by the observation of a high catalytic activity for complex [RhI(PPh3)2]2. New solution equilibrium studies on [RhX(PPh3)2]2 (X = Cl, I) in the presence of ligands of relevance to the catalytic reaction (PPh3, C2H4, PhNH2, X-, and the model Et2NH amine) are reported. Complex [RhCl(PPh 3)2]2 shows broadening of the 31P NMR signal upon addition of PhNH2, indicating rapid equilibrium with a less thermodynamically stable adduct. The reaction with Et2NH gives extensive conversion into cis-RhCl(PPh3)2(NHEt2), which is however in equilibrium with the starting material and free Et2NH. Excess NHEt2 yields a H-bonded adduct cis-RhCl(PPh3) 2(Et2NH) ·NHEt2, in equilibrium with the precursors, as shown by IR spectroscopy. The iodide analogue [RhI(PPh 3)2]2 shows less pronounced reactions (no change with PhNH2, less extensive addition of Et2NH with formation of cis-RhI(PPh3)2(NHEt2), less extensive reaction of the latter with additional Et2NH to yield cis-RhI(PPh3)2(Et2NH) ·NHEt2. The two [RhX(PPh3)2]2 compounds do not show any evidence for addition of the corresponding X- to yield a putative [RhX 2(PPh3)2]- adduct. The product of C 2H4 addition to [RhI(PPh3)2] 2, trans-RhI(PPh3)2(C2H 4), has been characterized in solution. Treatment of the RhCl 3·3H2O/PPh3/nBu4PI/PhNH 2 mixture under catalytic conditions yields mostly [RhCl(PPh 3)2]2, and no significant halide exchange, demonstrating that the promoting effect of iodide must take place at the level of high energy catalytic intermediates. The equilibria have also been investigated at the computational level by DFT with treatment at the full QM level including solvation effects. The calculations confirm that the bridge splitting reaction is slightly less favorable for the iodido derivative. Overall, the study confirms the active role of rhodium(I) species in ethylene hydroamination catalyzed by RhCl3·3H2O/PPh 3/nBu4PI and suggest that the catalyst resting state is [RhCl(PPh3)2]2 or its C2H4 adduct, RhCl(PPh3)2(C2H4), under high ethylene pressure.

Rhodium-catalyzed intermodular hydroiminoacylation of alkenes: Comparison of neutral and cationic catalytic systems

Both cationic and neutral rhodium catalytic systems for the hydroiminoacylation of alkenes were studied using NMR spectroscopy and DFT-based methods. With neutral systems, the oxidative addition step was shown to be thermodynamically favored. With the cat

Dehalogenation of hexachlorocyclohexanes and simultaneous chlorination of triethylsilane catalyzed by rhodium and ruthenium complexes

Complexes RhCl(PPh3)3 and RhH2Cl(P iPr3)2 catalyze the dehalogenation of γ-hexachloro-cyclohexane to benzene and the simultaneous chlorination of HSiEt3 to ClSiEt3. In

Direct reaction of photogenerated diarylcarbenes at square-planar rhodium(I)

A series of carbene complexes RhCl(CR′2)(PR 3)2 (R = Ph, Toi, Me, R′ = Ph and Tol) have been synthesised through direct reaction of photochemically generated free diarylcarbene with RhCl(CO)(PR3)2. This route to carbene complexes demonstrates the reactivity of simple diarylcarbenes towards transition metal complexes. The reactivity of some of these complexes towards H2, C2H4 and Et3SiH has been investigated.

Fluorous versions of Wilkinson's catalyst. Activity in fluorous hydrogenation of 1-alkenes and recycling by fluorous biphasic separation

Two novel fluorous tris(arylphosphine)rhodium(I) chloride complexes RhCl[P{C6H4-p-SiMe2(CH2)2C(n)F(2n+1)}3]3 (3a: n = 6, 3b: n = 8) being fluorous analogues of Wilkinson's catalyst show high activity in hydrogenation of 1-alkenes under single phase fluorous conditions and can be effectively recycled using the new concept of fluorous biphasic separation. For comparison the p-(trimethylsilyl)-substituted derivative RhCl[P(C6H4-p- SiMe3)3]3 (3c) has also been synthesized and the X-ray structure of dimeric [Rh(μ-Cl){P(C6H4p-SiMe3)3}2]2 (4c) was determined. A comparison of the catalytic activity of the fluorous catalysts and the nonfluorous derivatives under identical conditions revealed a decreasing activity in the order 3c > 3a > RhCl-(PPh3)3 > 3b. The recycling efficiency of the new catalysts (> 98% for 3b) is much better than expected on the basis of the fluorous phase affinity of the free phosphine ligands themselves and is in fact the result of the much higher fluorous phase affinity of the phosphine-containing rhodium species that are present during and after catalysis. Hence it is demonstrated that assembling multiple fluorous ligands in a specific configuration at one metal center can drastically improve the fluorous phase affinity of the resulting complexes.

Transfer-dehydrogenation of alkanes catalyzed by rhodium(I) phosphine complexes

Complexes of the form Rh(PMe3)2ClL' (L' = CO or trisubstituted phosphine) and [Rh(PMe3)2Cl]2 have previously been reported to catalyze the transfer-dehydrogenation of alkanes, using olefinic hydrogen acceptors under a dihydrogen atmosphere. Such complexes are herein reported to effect transfer-dehydrogenation in the absence of H2 but with much lower rates and total catalytic turnovers, even at much greater temperatures. Analogs with halides other than chloride (Br, I), or with pseudo-halides (OCN, N3), are found to exhibit generally similar behavior: high catalytic activity under H2 and measurable but much lower activity in the absence of H2. Thermolysis (under argon) of complexes [RhL2Cl]n (n = 1, 2; L is a phosphine bulkier than PMe3) in cyclooctane in the absence of hydrogen acceptors yielded cyclooctene. However, transfer-dehydrogenation was plagued by ligand decomposition. Under a hydrogen atmosphere complexes containing ligands much bulkier than PMe3 do not effect dehydrogenation. Complexes with tridentate ligands, η3-PXP)RhL' (PXP = (Me2PCH2Me2Si)2N, Me2PCH2(2,6-C6H3)CH2PMe2; L' = CO, C2H4), were also found to catalyze thermal or photochemical dehydrogenation of cyclooctane with limited reactivity. The structure of [Rh(PMe3)2Cl]2 was determined by single-crystal diffraction. The Rh(μ-Cl)2Rh bridge of 1 is folded like that of [Rh(CO)2Cl]2, unlike that of the planar PPh3 and PiPr3 analogs.

A high-yield conversion of trans-Rh(Cl)(CO)(PPh3)2 to Rh(Cl)(PPh3)3

The first high-yield procedure for conversion of trans-Rh(Cl)(CO)(PPh3)2 to Rh(Cl)(PPh3)3 has been achieved by utilization of the commercially available17 DPPA as a carbonyl ligand abstraction reagent.