Synthesis, characterisation and crystal structure of a dirhodium(II) compound with two bridging trifluoroacetamidate ligands

Daniels, Marcus A. M.; Mehmet, Nilgun; Tocher, Derek A.

doi:10.1039/dt9910002601

Cited by 8 publications

(6 citation statements)

References 20 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: 88%

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: 88%

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: 65%

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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“…The Rh-Rh distance (2.387(1) Å ) is the shortest [16] amongst similar paddlewheel Rh 2 (CH 3 COO) 2 complexes listed in Table 1. [17][18][19][20][21][22][23][24][25][26][27][28][29][30] It is our assertion that weak axial interactions lead to shorter metalmetal distance in compound 1. [8,9] The reaction of cis-[Ru 2 (CO) 4 (2) in high yield.…”

Section: Resultsmentioning

confidence: 93%

Contrasting Reactivity of 2-Mesityl-1,8-Naphthyridine (Mes-NP) with Singly-Bonded [RhII–RhII] and [RuI–RuI] Compounds

Saha¹,

Rahaman²,

Sinha³

et al. 2011

Aust. J. Chem.

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Reaction of cis-[Rh 2 (CH 3 COO) 2 (CH 3 CN) 6 ](BF 4 ) 2 with two equivalents of 2-mesityl-1,8-naphthyridine (Mes-NP) affords trans-[Rh 2 (CH 3 COO) 2 (Mes-NP) 2 ](BF 4 ) 2 (1). X-ray structure reveals weak Rh-C(ipso) interaction, and a short Rh-Rh distance. The same ligand, in contrast, oxidatively cleaves the Ru-Ru bond in cis-[Ru 2 (CO) 4 (CH 3 CN) 6 ](BF 4 ) 2 and results in trans-[Ru(Mes-NP) 2 (CH 3 CN) 2 ](BF 4 ) 2 (2). Both compounds adopt trans geometry to relieve the steric strain. Compound 2 exhibits moderate activity for the alcohol oxidation and aldehyde olefination reactions.

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Synthesis, characterisation and crystal structure of a dirhodium(II) compound with two bridging trifluoroacetamidate ligands

Cited by 8 publications

References 20 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

Contrasting Reactivity of 2-Mesityl-1,8-Naphthyridine (Mes-NP) with Singly-Bonded [RhII–RhII] and [RuI–RuI] Compounds

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