On rhodium(III) chloride complexes with N,N-dimethylformamide

Varshavskii, Yu. S.; Cherkasova, T. G.; Khrustalev, Victor N.; Podkorytov, Ivan S.; Nikol'skii, A. B.

doi:10.1134/s1070328407030074

Cited by 10 publications

(9 citation statements)

References 14 publications

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“…If the differences in the Rh-O distances and internal geometric parameters of carboxyl groups (the C-O bond lengths and OCO bond angles) are considered unessential, then, in the first approximation, the values of r and sin(θ/2) are expected to show a linear dependence. Data available in the literature [27][28][29][30][31][32][33][34] confirm this expectation (Fig. 2).…”

Section: Molecular and Crystal Structure Of [Rh(m-hcoo)(co) 2 ] 2 (I)supporting

confidence: 87%

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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Section: Molecular and Crystal Structure Of [Rh(m-hcoo)(co) 2 ] 2 (I)supporting

confidence: 87%

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

et al. 2005

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“…Data available in the literature [27][28][29][30][31][32][33][34] confirm this expectation (Fig. If the differences in the Rh-O distances and internal geometric parameters of carboxyl groups (the C-O bond lengths and OCO bond angles) are considered unessential, then, in the first approximation, the values of r and sin(θ/2) are expected to show a linear dependence.…”

Section: Molecular and Crystal Structure Of [Rh(m-hcoo)(co) 2 ] 2 (I)mentioning

confidence: 66%

“…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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“…We believe the concerted reduction of two Rh(III) atoms with one carbonyl group to be preferable in the synthesis of dirhodium(II) tetraacetate by the procedure we proposed [39]. In the presence of large excess of acetate anion in the rhodium(III) chloride DMF solution, the binuclear species should be stabilized by acetate bridges, and in this case the combination of two rhodium(III) atoms may act as a united two-electron oxidant toward one carbonyl group (apparently bridging in this case, Rh-(CO)-Rh).…”

Section: Oxidative/reductive Hydrolysis Of [Rh III (Co) 2 Cl 3 ] 2 Asmentioning

confidence: 97%

“…Other solvents were purified according to standard procedures [40]. Known complexes were synthesized by published procedures: Rh(Acac) 3 [41], Rh 2 (RCOO) 4 (H 2 O) 2 [39], [Rh(CO) 2 Cl 3 ] 2 [37], RhCl 3 -(DMSO) 3 [42a], RhCl 3 (DMSO) 2 (DMF) [42], RhCl(PPh 3 ) 3 [43]. In the synthesis of RhCl 3 (CH 3 CN) 3 (a mixture of mer and fac isomers) we followed general instructions given in the works [44] and have obtained several preparations of required composition and slightly different IR spectra.…”

Section: Preparation Of Starting Materialsmentioning

confidence: 99%

Remarks on the process of homogeneous carbonylation of rhodium compounds by N,N-dimethylformamide

Varshavsky

Cherkasova

2007

Journal of Organometallic Chemistry

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On rhodium(III) chloride complexes with N,N-dimethylformamide

Cited by 10 publications

References 14 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

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

Remarks on the process of homogeneous carbonylation of rhodium compounds by N,N-dimethylformamide

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