Hydration and reduction of carbon dioxide by rhodium hydride compounds. Preparation and reactions of rhodium bicarbonate and formate complexes, and the molecular structure of RhH2(O2COH)(P(i-Pr)3)2

Yoshida, T.; Thorn, David L.; Okano, Tamon; Ibers, James A.; Otsuka, Sei

doi:10.1021/ja00509a029

Cited by 109 publications

(52 citation statements)

References 18 publications

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“…[HRhL n ] + CO 2 conversion observed by Leitner and other authors [5,6]. Mechanistic aspects of related reactions and of the reverse CO 2 insertion into the M-H bond are discussed extensively [5][6][7][8][9][10][11][12].…”

mentioning

confidence: 92%

Action of triphenylphosphine on [Rh(HCOO)(PPh3)2(CO)]. A novel synthetic route to [HRh(PPh3)3(CO)]

Varshavsky

Cherkasova

Podkorytov

2004

Inorganic Chemistry Communications

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mentioning

confidence: 92%

Action of triphenylphosphine on [Rh(HCOO)(PPh3)2(CO)]. A novel synthetic route to [HRh(PPh3)3(CO)]

Varshavsky

Cherkasova

Podkorytov

2004

Inorganic Chemistry Communications

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“…The 31 P NMR data also turned sensitive to the electronic effect of substituent in carboxylate group: as its electronegativity increases, δ 31 P and 1 J(PRh) decrease. As it is always observed, the ν(CO) values in IR spectra of triphenylphosphine complexes IV-VI are considerably higher than those in the spectra of analogous complexes with aliphatic phosphines PCy 3 (Cy is cyclohexyl), PiPr 3 [15,18,19,43,44].…”

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

confidence: 80%

“…The possible mechanisms of these reactions and of reversible reactions of CO 2 introduction at a metal-hydrogen bond were extensively discussed in the literature [16,18,[50][51][52][53][54][55].…”

Section: Hrh(pph 3 ) 3 (Co) + Comentioning

confidence: 99%

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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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“…Perspektivische Ansicht der Molekülstruktur von 6 (a; HB: gestrichelte Linie); ausgewählte Bindungslängen (Å ) und -winkel (°) des chelatisierend koordinierenden Hydrogencarbonats (b; normalfett: d. A.; kursiv:[37]; normal:[22]; kursivfett:[21]); Ansicht eines π-π'-Dimers in 6 (c) die für die Anordnung der Komponenten im Feststoff ebenfalls Bedeutung haben. Die kürzesten (O···C)-Abstände findet man zwischen O2 und C47 des Kations (N10) mit 3,26(1) Å und zwischen O5 und C33 bzw.…”

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Phthalocyaninate und Tetraphenylporphyrinate von hochkoordiniertem ZrIV/HfIV mit Hydroxo-, Chloro-, (Di)Phenolato-, (Hydrogen)Carbonato- sowie (Amino)Carboxylato-LigandenProfessor Joachim Strähle zum 65. Geburtstag gewidmet

Tutaß¹,

Klöpfer²,

Hückstädt³

et al. 2002

Z. anorg. allg. Chem.

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Hydration and reduction of carbon dioxide by rhodium hydride compounds. Preparation and reactions of rhodium bicarbonate and formate complexes, and the molecular structure of RhH2(O2COH)(P(i-Pr)3)2

Cited by 109 publications

References 18 publications

Action of triphenylphosphine on [Rh(HCOO)(PPh3)2(CO)]. A novel synthetic route to [HRh(PPh3)3(CO)]

Action of triphenylphosphine on [Rh(HCOO)(PPh3)2(CO)]. A novel synthetic route to [HRh(PPh3)3(CO)]

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

Phthalocyaninate und Tetraphenylporphyrinate von hochkoordiniertem ZrIV/HfIV mit Hydroxo-, Chloro-, (Di)Phenolato-, (Hydrogen)Carbonato- sowie (Amino)Carboxylato-LigandenProfessor Joachim Strähle zum 65. Geburtstag gewidmet

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