Catalysis by metal complexes

Svoboda, P.; Belopotapova, T.S.; Hetflejš, J.

doi:10.1016/s0022-328x(00)91257-9

Cited by 47 publications

(2 citation statements)

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“…To the best of our knowledge the only previous reports of similar reactions are the reaction of RhCl(PPh3)3 with H2 and C02 at high pressure and 100 °C to give RhCl(CO)(PPh3)220 and the formation of RhCI(CO)(PPh3)2 from RhClH(Si(OEt)3)-(PPh3)2 and C02. 61 The reverse reaction, the formation of H2 and C02 from H20 and CO, is the well-known water-gas shift reaction. Since the water-gas shift reaction is thermodynamically favorable and is readily catalyzed by Rh(I)-hydride complexes,19 it is very surprising that the formation of a Rh(I)-carbonyl complex from C02and a Rh(IlI)-dihydride complex is also thermodynamically favorable.…”

Section: Resultsmentioning

confidence: 99%

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

Yoshida¹,

Thorn²,

Okano³

et al. 1979

J. Am. Chem. Soc.

109

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Reaction of Rh(I) -hydride complexes RhH(P(z'-Pr)3)3, RhH(N2)(PPh(r-611)2)2, and Rh2H2(q-N2)(P(c-C6Hl ,)3)4 with CO? in the presence of H?0 has been found to afford novel dihydrido bicarbonato complexes RhH2(0?C0H)L2 (1, L = P(/-Pr)3; 2, L = PPh(r-Bu)2; 3, L = P(c-C6H 11)3). The crystal and molecular structure of 1 has been determined at -160 °C.The complex RhH2(0?COH)(P(/-Pr)3)2 (1) crystallizes in the monoclinic space group C\h-P2\/c, with four formula units in a cell of dimensions a = 15.82 (I) Á, b = 10.88 (1) A, c = I 5.49 (1) Á, ß = 1 14.5 (1)°, V = 2428 Á3. In the solid state 1 consists of distorted octahedral Rh(III) centers coupled by intermolecular hydrogen bonding between bicarbonato ligands. These dihydrido bicarbonato complexes, and analogous dihydrido formato complexes, reduce C02 to form Rh(l) carbonyl bicarbonato and formato complexes and H20. 1587 s b 1338 s 792 m RhH2(02C0H)[PPh(z-Bu)2]2 (2) 2145 m,2220 m 2660 m 1583 s b 1340 s 802 m RhH2(02C0H)[P(c-C6HM)3]2(3)2138 m, 2158 m( (2110, 2160) 2640 m 1585 s 1410 w 1340 s 790 m Rh(C0)(02C0H)[P(c-C6Hn)3]2(6) 1942 s 2650 w 1608 s 1420 s 1355 s 821 m Rh(C0)(02C0D)[P(c-C6Hn)3]2 1942 s 2087 w 1590 s 1062 s 1405 s 821 m Rh(13CO)(G2'3COH)[P(c-C6H,,),]2 1900 s 2657 w 1575 s 1402 w 1345 s 822 m Rh(CO)(02COH)[P(Z-Pr)3]2 (7) 1952 s 2600 w 1615 s 1413 s 1350 s 823 m Rh(C0)(02C0H)(PPh3), 1968 s 2650 w 1600 s 1430 sd 1350 s 819 m (OsCOH)22" <• 2620 w 1618 s 1405 s 1367 s 830 m (OsCOD)22" f 2055 w 1615 s 1050 s 1392 s 830 m "stretching; 5, in-plane bending; tt, out-of-plane bending. * The band probably overlaps with that of Nujol. ' Sample recrystallized from toluene. The value in parentheses is for the sample recrystallized from THF. d The band is a composite of 50ho and Pp-ph. *' Reference 46.

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Section: Resultsmentioning

confidence: 99%

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

Yoshida¹,

Thorn²,

Okano³

et al. 1979

J. Am. Chem. Soc.

109

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“…If one generates in a chemical ionization source the "mixed" complex Fe+(CH3NC) (CD3CN), the only product observed8 in the MI spectrum of this mass-selected species is due to the loss of CD3CN proving13 that BE(Fe+- (5) Czekay, G.; Drewello, T.; Eller, K.; Zummack, W.; Schwarz, H. Organometallics, in press. (6) Stepnowski, R. M.; Allison, J. Organometallics 1988, 7, 2097. (7) In their analysis, the authors (Radecki, B. D.; Allison, J. Organometallics 1986, 5, 411) note that, for alkanes, the preference of insertion of M+ into a particular skeleton bond A-B increases with decreasing ionization energies of the corresponding "radicals" A' and B".…”

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The detailed mechanism for the reaction of bare iron(I) ions with tert-butyl cyanide and isocyanide in the gas phase

Eller¹,

Schwarz²

1989

Organometallics

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Experimental evidence is presented demonstrating that bare Fe+ does not insert in the C-X bond of (CH,),C-X (X = CN, NC). Rather, initial "end-on" complexation of the functional group induces cleavage of this bond which is followed by hydrogen transfer to X; this results in the formation of diligated complexes of the general structure C,H,-.M+-.XH (Scheme 111, 9 and 12). These intermediates serve as precursors for the competitive loss of C, H, and HX; by means of high-energy collisional activation the products due to the unimolecular elimination of C4H, are characterized by MS/MS techniques as the "end-on" complexes of HCN and HNC with Fe' (10 and 13, respectively). Moreover, new insight into the mechanism of "dissociative attachment" is provided.

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Chlorotris(Triphenylphosphine)Rhodium(I): Its Chemical and Catalytic Reactions

Jardine

1981

Progress in Inorganic Chemistry

118

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Catalysis by metal complexes

Cited by 47 publications

References 2 publications

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

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

The detailed mechanism for the reaction of bare iron(I) ions with tert-butyl cyanide and isocyanide in the gas phase

Chlorotris(Triphenylphosphine)Rhodium(I): Its Chemical and Catalytic Reactions

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