The reaction of [HFe(CO)4]- with Ir(CO)3Br (in molar ratio 3:1) produced [HFe3Ir(CO)12]2- (1), which reacts with acids to yield the dihydride complex. [H2Fe3Ir(CO)12]- (2). The salt [NEt4]2[HFe3Ir(CO)12] crystallizes in the orthorhombic space group Pnma, with a = 20.346 (7) angstrom, b = 15.135 (2) angstrom, c = 11.807 (5) angstrom, V = 3636 (1) angstrom 3, and Z = 4; a full structural determination was prevented by the poor quality of the crystals. The reaction of [FeIr4(CO)15]2- with [Ir(CO)4]-, in refluxing acetonitrile, has yielded the new compound [FeIr5(CO)15]3- (3). The trianion reacts with stoichiometric amount of H+ to form [HFeIr5(CO)15]2- (4) and with acids in excess to yield the corresponding dihydride derivative [H2FeIr5(CO)15]- (5), which, at room temperature, is not stable and is readily transformed into [FeIr5(CO)16]- (6). The salts of 3, 4, and 6 were characterized by single-crystal X-ray analyses. [NEt4]3[FeIr5(CO)15] crystallizes in the triclinic space group P1BAR, with a = 18.827 (5) angstrom, b = 19.476 (6) angstrom, c = 18.064 (5) angstrom alpha = 117.06 (3)-degrees, beta = 90.76 (2)-degrees, gamma = 61.71 (2)-degrees, and Z = 4. The octahedral carbonyl cluster contains 12 terminal and three edge-bridging carbonyl groups. [NMe3(CH2Ph)]2[HFeIr5(CO)15] crystallizes in the triclinic space group P1BAR, with a = 10.218 (3) angstrom, b = 10.989 (4) angstrom, c = 20.757 (5) angstrom, alpha = 101.07 (2)-degrees, beta = 97.61 (2)-degrees, gamma = 108.13 (2)-degrees, and Z = 2. The octahedral metal framework of the hydrido carbonyl cluster is surrounded by 11 terminal and four edge-bridging carbonyl groups; the hydrogen atom was located from the X-ray data and it is terminally bonded to iridium with a Ir-H distance of 1.60 (9) angstrom. [NMe3(CH2Ph)] [FeIr5(CO)16] crystallizes in the triclinic space group P1BAR, with a = 9.727 (2) angstrom, b = 16.296 (2) angstrom, c = 22.056 (2) angstrom, alpha = 79.99 (2)-degrees, beta = 80.61 (2)-degrees, gamma = 83.83 (1)-degrees, and Z = 4. The metal carbonyl cluster possess a metal cage based on an octahedral unit surrounded by 12 terminal and four face bridging carbonyl groups. The electrochemical study of the redox propensity of [FeIr5(CO)16]- and [FeIr5(CO)15]3- allowed us to elucidate the mechanistic aspects of their interconversion.

IRON IRIDIUM MIXED-METAL CARBONYL CLUSTERS .3. SYNTHESIS, CHEMICAL CHARACTERIZATION, ELECTROCHEMICAL-BEHAVIOR, AND SOLID-STATE STRUCTURES OF [NET4]3[FEIR5(CO)15], [NME3(CH2PH)]2[HFEIR5(CO)15], AND [NME3(CH2PH)][FEIR5(CO)16] - SPECTROSCOPIC AND CHEMICAL EVIDENCE FOR THE EXISTENCE OF [HFE3IR(CO)12]2-, [H2FE3IR(CO)12]-, AND [H2FEIR5(CO)15]- / A. CERIOTTI, R. DELLAPERGOLA, L. GARLASCHELLI, F. LASCHI, M. MANASSERO, N. MASCIOCCHI, M. SANSONI, P. ZANELLO. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 30:17(1991), pp. 3349-3357.

IRON IRIDIUM MIXED-METAL CARBONYL CLUSTERS .3. SYNTHESIS, CHEMICAL CHARACTERIZATION, ELECTROCHEMICAL-BEHAVIOR, AND SOLID-STATE STRUCTURES OF [NET4]3[FEIR5(CO)15], [NME3(CH2PH)]2[HFEIR5(CO)15], AND [NME3(CH2PH)][FEIR5(CO)16] - SPECTROSCOPIC AND CHEMICAL EVIDENCE FOR THE EXISTENCE OF [HFE3IR(CO)12]2-, [H2FE3IR(CO)12]-, AND [H2FEIR5(CO)15]-

A. CERIOTTI
Primo
;
L. GARLASCHELLI;M. MANASSERO;M. SANSONI
Penultimo
;
1991

Abstract

The reaction of [HFe(CO)4]- with Ir(CO)3Br (in molar ratio 3:1) produced [HFe3Ir(CO)12]2- (1), which reacts with acids to yield the dihydride complex. [H2Fe3Ir(CO)12]- (2). The salt [NEt4]2[HFe3Ir(CO)12] crystallizes in the orthorhombic space group Pnma, with a = 20.346 (7) angstrom, b = 15.135 (2) angstrom, c = 11.807 (5) angstrom, V = 3636 (1) angstrom 3, and Z = 4; a full structural determination was prevented by the poor quality of the crystals. The reaction of [FeIr4(CO)15]2- with [Ir(CO)4]-, in refluxing acetonitrile, has yielded the new compound [FeIr5(CO)15]3- (3). The trianion reacts with stoichiometric amount of H+ to form [HFeIr5(CO)15]2- (4) and with acids in excess to yield the corresponding dihydride derivative [H2FeIr5(CO)15]- (5), which, at room temperature, is not stable and is readily transformed into [FeIr5(CO)16]- (6). The salts of 3, 4, and 6 were characterized by single-crystal X-ray analyses. [NEt4]3[FeIr5(CO)15] crystallizes in the triclinic space group P1BAR, with a = 18.827 (5) angstrom, b = 19.476 (6) angstrom, c = 18.064 (5) angstrom alpha = 117.06 (3)-degrees, beta = 90.76 (2)-degrees, gamma = 61.71 (2)-degrees, and Z = 4. The octahedral carbonyl cluster contains 12 terminal and three edge-bridging carbonyl groups. [NMe3(CH2Ph)]2[HFeIr5(CO)15] crystallizes in the triclinic space group P1BAR, with a = 10.218 (3) angstrom, b = 10.989 (4) angstrom, c = 20.757 (5) angstrom, alpha = 101.07 (2)-degrees, beta = 97.61 (2)-degrees, gamma = 108.13 (2)-degrees, and Z = 2. The octahedral metal framework of the hydrido carbonyl cluster is surrounded by 11 terminal and four edge-bridging carbonyl groups; the hydrogen atom was located from the X-ray data and it is terminally bonded to iridium with a Ir-H distance of 1.60 (9) angstrom. [NMe3(CH2Ph)] [FeIr5(CO)16] crystallizes in the triclinic space group P1BAR, with a = 9.727 (2) angstrom, b = 16.296 (2) angstrom, c = 22.056 (2) angstrom, alpha = 79.99 (2)-degrees, beta = 80.61 (2)-degrees, gamma = 83.83 (1)-degrees, and Z = 4. The metal carbonyl cluster possess a metal cage based on an octahedral unit surrounded by 12 terminal and four face bridging carbonyl groups. The electrochemical study of the redox propensity of [FeIr5(CO)16]- and [FeIr5(CO)15]3- allowed us to elucidate the mechanistic aspects of their interconversion.
Settore CHIM/03 - Chimica Generale e Inorganica
1991
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/189991
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