440. Carbonyl complexes of rhodium. Part I. Complexes with triarylphosphines, triarylarsines, and triarylstibines

Vallarino, L. M.

doi:10.1039/jr9570002287

Cited by 119 publications

(22 citation statements)

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“…The parent member of this series, 1-[Cl-Ph], was first synthesized in 1957 and is one of the best known complexes of rhodium(). 16 This complex is readily formed from RhCl(PPh 3 ) 3 by CO addition or aldehyde decarbonylation, 17 undergoes facile photodissociation of CO and functions as a photo-catalyst for benzene carbonylation. 18, 19 However, in contrast to its iridium() analogue, Vaska's complex, which oxidatively adds H 2 readily with an equilibrium constant of >10 3 , 20 RhCl-(CO)(PPh 3 ) 2 had not previously been seen to react with dihydrogen directly.…”

Section: Introductionmentioning

confidence: 99%

Activation of H2 by halogenocarbonylbis(phosphine)rhodium(I) complexes. The use of parahydrogen induced polarisation to detect species present at low concentration

Morran¹,

Duckett²,

Howe³

et al. 1999

J. Chem. Soc., Dalton Trans.

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Complexes of the form RhX(CO)(PR 3 ) 2 [X = Cl, Br or I; R = Me or Ph] reacted with H 2 to form a series of binuclear complexes of the type (PR 3 ) 2 H 2 Rh(µ-X) 2 Rh(CO)(PR 3 ) [X = Cl, Br or I, R = Ph; X = I, R = Me] and (PMe 3 ) 2 (X)-HRh(µ-H)(µ-X)Rh(CO)(PMe 3 ) [X = Cl, Br or I] according to parahydrogen sensitised 1 H, 13 C, 31 P and 103 Rh NMR spectroscopy. Analogous complexes containing mixed halide bridges (PPhare detected when RhX(CO)(PPh 3 ) 2 and RhY(CO)(PPh 3 ) 2 are warmed together with p-H 2 . In these reactions only one isomer of the products (PPh 3 ) 2 H 2 Rh(µ-I)(µ-Cl)Rh(CO)(PPh 3 ) and (PPh 3 ) 2 H 2 Rh(µ-I)-(µ-Br)Rh(CO)(PPh 3 ) is formed in which the µ-iodide is trans to the CO ligand of the rhodium() centre. When (PPh 3 ) 2 H 2 Rh(µ-Cl)(µ-Br)Rh(CO)(PPh 3 ) is produced in the same way two isomers are observed. The mechanism of the hydrogen addition reaction is complex and involves initial formation of RhH 2 X(CO)(PR 3 ) 2 [R = Ph or Me], followed by CO loss to yield RhH 2 X(PR 3 ) 2 . This intermediate is then attacked by the halide of a precursor complex to form a binuclear species which yields the final product after PR 3 loss. The (PPh 3 ) 2 H 2 Rh(µ-X) 2 Rh(CO)(PPh 3 ) systems are shown to undergo hydride self exchange by exchange spectroscopy with rates of 13.7 s Ϫ1 for the (µ-Cl) 2 complex and 2.5 s Ϫ1 for the (µ-I) 2 complex at 313 K. Activation parameters indicate that ordering dominates up to the rate determining step; for the (µ-Cl) 2 system ∆H ‡ = 52 ± 9 kJ mol Ϫ1 and ∆S ‡ = Ϫ61 ± 27 J K Ϫ1 mol Ϫ1 . This process most likely proceeds via halide bridge opening at the rhodium() centre, rotation of the rhodium() fragment around the remaining halide bond and bridge re-establishment. If the triphenylphosphine ligands are replaced by trimethylphosphine distinctly different reactivity is observed. When RhX(CO)(PMe 3 ) 2 [X = Cl or Br] is warmed with p-H 2 the complex (PMe 3 ) 2 (X)HRh(µ-H)(µ-X)Rh(CO)(PMe 3 ) [X = Cl or Br] is detected which contains a bridging hydride trans to the rhodium() PMe 3 ligand. However, when X = I, the situation is far more complex, with (PMe 3 ) 2 H 2 Rh(µ-I) 2 Rh(CO)(PMe 3 ) observed preferentially at low temperatures and (PMe 3 ) 2 (I)HRh(µ-H)-(µ-I)Rh(CO)(PMe 3 ) at higher temperatures. Additional binuclear products corresponding to a second isomer of (PMe 3 ) 2 (I)HRh(µ-H)(µ-I)Rh(CO)(PMe 3 ), in which the bridging hydride is trans to the rhodium() CO ligand, and (PMe 3 ) 2 HRh(µ-H)(µ-I) 2 Rh(CO)(PMe 3 ) are also observed in this reaction. The relative stabilities of related systems containing the phosphine PH 3 have been calculated using approximate density functional theory. In each case, the (µ-X) 2 complex is found to be the most stable, followed by the (µ-H)(µ-X) species with hydride trans to PH 3 .

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Section: Introductionmentioning

confidence: 99%

Activation of H2 by halogenocarbonylbis(phosphine)rhodium(I) complexes. The use of parahydrogen induced polarisation to detect species present at low concentration

Morran¹,

Duckett²,

Howe³

et al. 1999

J. Chem. Soc., Dalton Trans.

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“…Here also, the stibine-stabilized complex was air-sensitive. Similar gradations ofproperties have been found for carbonyl complexes of vanadium (8), nickel (9), and rhodium (10). Indeed, it is well-known (11) that, although the differences in electronegativity are not great, the order of co-ordinating affinities of Group V atoms in donor ligands is P > As > Sb > Bi.…”

Section: Resultsmentioning

confidence: 57%

Chemistry of metal hydrides. VI. Cationic platinum(II) carbonyls stabilized with tertiary arsines and stibines

Cherwinski¹,

Clark²

1969

Can. J. Chem.

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The synthesis of [PtzCI,(R3M),][BF4]z, and its cleavage with carbon monoxide to form the cationic carbonyl species [PtC1(CO)(R3M),]+ is described for R = ethyl or phenyl, and M = As or Sb. A comparison of the physical properties and spectroscopic data of these compounds, and the analogues for M = P is made with related complexes of other transition metals. Unlike their phosphine analogues, these species and the stibine-stabilized cationic carbonyls do not produce the corresponding hydrides on reaction with water in the presence of a salt catalyst. These differences in chemical reactivity are related to the basicity of the ligands.

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“…Komplekse met die algemene formule trans-[Rh(CO)X(L) 2 ] (X = halied of pseudo-halied; L = ariel of alkiel gesubstitueerde tersiêre fosforligand) word in baie gevalle verwys na as Vaskatipe komplekse (Ohgomori & Watanabe, 1990, Galding et al, 2016, Smoleński et al, 2011, Roodt et al, 2003, 'n naam wat verband hou met die werk van Vaska & DiLuzio, 1961 op die oorspronklike trans-[Ir(CO)Cl(PPh 3 ) 2 ] kompleks. Die geskiedenis agter die benaming is ietwat omstrede, aangesien Angoletta, 1959 alreeds die kompleks twee jaar voor die werk van Vaska en DiLuzio berei het, en selfs die rhodium-analoog was alreeds gerapporteer (Vallarino, 1957) en is in 'n mate deur Chatt en mede-werkers ondersoek (Winterton & Leigh, 2002). Die volgorde van gebeure wat tot die vaspen van die naam gelei het, word uiteengesit in 'n 50 ste herdenkingsartikel van die kompleks (Kirss, 2013); die redes word hoofsaaklik toegeskryf aan vroeëre, verkeerde identifi sering van die verbinding asook die wyer impak van die tydskrif wat Vaska gebruik het.…”

Section: Inleidingunclassified

Chloro-karboniel vastetoestand-wanordebepaling in Vaska tipe komplekse

Muller

2020

SATNT

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‘n Ondersoek na die effek van gemengde feniel-sikloheksiel gesubstitueerde ariel tersiêre fosfiene op die vastetoestandwanorde van die Cl–Rh–CO-groep in Vaska-tipe komplekse trans-[M(CO)Cl(PPhnCy3-n)2], waar M = Rh(I) of Ir(I), Ph = C6H5, Cy = C6H11 en n = 1 of 2, word aangebied. Enkelkristal X-straalstrukture van 4 voorbeelde van die reeks word geraporteer en vergelyk met verwante strukture wat dikwels die wanorde van die Cl–Rh–CO-groep, wat deur kristallografiese simmetrie beheer word, openbaar. Digtheids funksionele teorie (DFT) geometrie-optimalisering en energieberekenings op konformere van hierdie komplekse dui aan dat die wanorde waarskynlik is. ‘n Onverwagte vastetoestandwanorde tussen feniel- en sikloheksielsubstituente van die fosfi ene word ook bespreek.

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440. Carbonyl complexes of rhodium. Part I. Complexes with triarylphosphines, triarylarsines, and triarylstibines

Cited by 119 publications

References 0 publications

Activation of H2 by halogenocarbonylbis(phosphine)rhodium(I) complexes. The use of parahydrogen induced polarisation to detect species present at low concentration

Activation of H2 by halogenocarbonylbis(phosphine)rhodium(I) complexes. The use of parahydrogen induced polarisation to detect species present at low concentration

Chemistry of metal hydrides. VI. Cationic platinum(II) carbonyls stabilized with tertiary arsines and stibines

Chloro-karboniel vastetoestand-wanordebepaling in Vaska tipe komplekse

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