A comprehensive study of the system μ-dichlorotetra-carbonyldirhodium-phosphines and evidence of oxidative addition involving new dinuclear complexes

Gallay, Jacques; Montauzon, Dominique de; Poilblanc, R.

doi:10.1016/s0022-328x(00)81375-3

Cited by 71 publications

(12 citation statements)

References 16 publications

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“…The above assignment of the 13 C and 31 P signals is based on the comparison of their relative intensities and was performed taking into account data in [45,62,63] for the analogous complexes occurring in the reaction mixtures [Rh(µ-Cl)(CO) 2 of the products is assigned to dicarbonyl fragment in composition Y 1 ; doublets of doublets with higher δ 13 C belong to monocarbonyl fragments in composition Y 1 and Y 2 . Broadening of signal at 190.1 ppm corresponding to complex V is likely to be explained by some exchange processes in a solution.…”

Section: Reaction Of [Rh(m-ch 3 Coo)(co) 2 ] 2 With Pphmentioning

confidence: 99%

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

et al. 2005

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Complexes [Rh(µ-RCOO)(CO) 2 ] 2 , where R = H, CH 3 , CF 3 (I, II, III, respectively) are synthesized by reacting anhydrous carboxylic acids with Rh(Acac)(CO) 2 crystals. In compounds I, II, III, and trans-Rh(RCOO)(PPh 3 ) 2 (CO), where R = H, CH 3 , CF 3 (IV, V, VI, respectively), ν(CO) and 1 J(CRh) increase and δ 13 C decreases with the increasing electronegativity of R (CH 3 < H < CF 3 ). In the case complexes IV, V, and VI, the values of δ 31 P and 1 J(PRh) decrease in the same order. Complexes I and V are studied by X-ray diffraction analysis. Intramolecular (2.946 Å) and intermolecular (3.127 Å) Rh-Rh distances in a columnar structure I are close, i.e., the structure contains infinite chains of metal atoms. Interaction of IV with chlorinated solvents results in trans-RhCl(PPh 3 ) 2 (CO). When heated with an excess of PPh 3 in propanol-2, compound IV transforms to HRh(PPh 3 ) 3 (CO). The latter reaction was suggested as a basis of a new method that can be used to obtain HRh(PPh 3 ) 3 (CO).

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Section: Reaction Of [Rh(m-ch 3 Coo)(co) 2 ] 2 With Pphmentioning

confidence: 99%

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

et al. 2005

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“…Triphenylphosphane and styrene were purchased from Sigma-Aldrich and used as received. [Rh(CO) 2 Cl] 2 , [14] [RhA C H T U N G T R E N N U N G (NBD) 2 ]BF 4 , [15] (p-anisyl)diphenylphosphane, [3b] and the phosphane selenides [16] were prepared according to the literature. Sulfonation of (p-anisyl)diphenylphosphane was published earlier.…”

Section: Experimental Section General Remarksmentioning

confidence: 99%

Facile Synthesis of a Monosulfonated Triphenylphosphane (TPPMS) Derived Ligand having Strong π‐Acceptor Character

Gulyás¹,

Bacsik

Szöllősy

et al. 2006

Adv Synth Catal

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Two phenyl rings of triphenylphosphane have been modified by electron-withdrawing trifluoromethyl groups. A methoxy group has been introduced at the para-position of the third ring. Due to the activating effect of the methoxy group, the phosphane can be monosulfonated under mild conditions and with complete selectivity. The novel ligand, sodium 5-[bis-(4-trifluoromethylphenyl)-phosphanyl]-2-methoxybenzenesulfonate, has been obtained in quantitative yield, and it has an outstanding p-acceptor capacity among the known sulfonated triarylphosphanes. It is not soluble in water but soluble in light alcohols and ionic liquids. Its solubility properties allow facile catalyst separation without water.

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Section: Reaction Of [Rh(m-ch 3 Coo)(co) 2 ] 2 With Pphmentioning

confidence: 99%

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

et al. 2005

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Dirhodium(I) di( µ -carboxylato) tetracarbonyls[ Rh ( µ -RCOO )( CO ) 2 ] 2 were obtained for the first time by reacting rhodium(I) carbonyl chloride dimer [ Rh ( µ -Cl )( CO ) 2 ] 2 with silver carboxylates [1]. The authors [1] synthesized and characterized acetate, trifluoroacetate, p -fluorobenzoate, and phthalate complexes of this type and some bis(phosphine) derivatives, such as transRh ( RCOO )( PPh 3 ) 2 ( CO ) . Later, some other methods were developed for synthesizing [ Rh ( µ -RCOO )( CO ) 2 ] 2 complexes with R = CH 3 ( II ), CF 3 ( III ) [2-4] and their monocarbonyl triphenylphosphine derivatives transRh ( RCOO )( PPh 3 ) 2 ( CO ) [2,[5][6][7][8][9][10][11][12]. The authors of [4] reported the results of X-ray diffraction study of [ Rh ( µ -The structure of transRh ( CF 3 COO )( PPh 3 ) 2 ( CO ) was previously determined in [13].Rhodium(I) formate complexes became available considerably later. Thus, the carbonyl formate dimer [ Rh ( µ -HCOO )( CO ) 2 ] 2 ( I ) was synthesized for the first time via a reaction of dirhodium(II) tetraacetate with carbon monoxide in formic acid [14]. Some other methods of synthesis of this compound were reported later on in [15,16]. A series of bis(phosphine) complexes trans -Rh ( HCOO )( PR 3 ) 2 ( CO ) was also synthesized [17][18][19]. The molecular structure of transRh ( HCOO )( PPh 3 ) 2 ( CO ) ( IV ) was determined by X-ray diffraction method [17]. It should be noted that in subsequent years, rhodium(I) formate complexes with carbonyl and some other π -acceptor ligands (olefins, phosphines) were studied more intensively than other carboxylate derivatives. This is quite natural, since formate group is a C 1 ligand with composite structure and high reactivity.It is noteworthy that though separate IR and NMR parameters of Rh(I) carbonyl carboxylate complexes were reported in some of the above-mentioned papers, their comparison is difficult, since they were determined under different conditions. In this work, simple reaction is suggested that can be used to synthesize [ Rh ( µ -HCOO )( CO ) 2 ] 2 complex and its crystal structure is determined. The latter complex is shown to be suitable starting reagent in synthesis of Rh(I) carbonyl hydride HRh ( PPh 3 ) 3 ( CO ) . X-ray diffraction data available in the literature for bis(triphenylphosphine) complexes of the composition transRh ( RCOO )( PPh 3 ) 2 ( CO ) with R = H, CF 3 [13, 17] are supplemented with the data we obtained for analogous acetate complex. IR and NMR measurements of carbonyl formate complexes [ Rh ( µ -HCOO )( CO ) 2 ] 2 and of trans -Rh ( HCOO )( PPh 3 ) 2 ( CO ) together with their acetate and trifluoroacetate analogs made it possible to obtain for the first time a set of comparable spectral parameters that indicates a transfer of electronic effects of the ligands through a central atom. The results of this work were partially reported in the previous publications [20][21][22]. Abstract-Complexes[Rh(µ-RCOO)(CO) 2 ] 2 , where R = H, CH 3 , CF 3 (I, II, III, respectively) are synthesized by reacting anhyd...

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A comprehensive study of the system μ-dichlorotetra-carbonyldirhodium-phosphines and evidence of oxidative addition involving new dinuclear complexes

Cited by 71 publications

References 16 publications

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

Facile Synthesis of a Monosulfonated Triphenylphosphane (TPPMS) Derived Ligand having Strong π‐Acceptor Character

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

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