Iridium- and Rhodium-Initiated C-C Coupling of Carbon Dioxide with Malonodinitrile

Arno Behr; Eberhardt Herdtweck; Wolfgang A. Herrmann; Wilhelm Keim; Walter Kipshagen

doi:10.1021/om00154a007

Iridium- and Rhodium-Initiated C-C Coupling of Carbon Dioxide with Malonodinitrile

Arno Behr, Eberhardt Herdtweck, Wolfgang A. Herrmann, Wilhelm Keim, Walter Kipshagen

Technische Universität München

Publikation: Beitrag in Fachzeitschrift › Artikel › Begutachtung

26 Zitate (Scopus)

Abstract

Electron-rich complexes of iridium(I) and rhodium(I) react with activated alkanes such as malonodinitrile and carbon dioxide under C-C coupling to give compounds of the general formula [L_nMXH]⁺[O₂CCH(CN)₂]- (L = PMe₃, n = 4; L = dmpe or depe, n = 2; X = Cl, H; M = Ir, Rh). The influence of the different phosphorus ligands on the structures of the complexes is described. Compounds [Hlr-(depe)₂Cl]⁺[O₂CCH(CN)₂]- (1) and [H₂Ir(PMe₃)₄]⁺[0₂CCH(CN)₂]- (4) have been characterized by X-ray structure analyses which both show the dicyanoacetate anions to be dimeric via hydrogen bonds in the crystal form. To study the reaction mechanism the complexes HIr(PMe₃)₄and [Ir(depe)₂]Cl were reacted in the absence of carbon dioxide with malonodinitrile and yielded the C-H activated malonodinitrile anion complexes [H₂Ir(PMe₃)₄]⁺[CH(CN)₂]- (5) (X-ray structure determination confirms the supposed molecular structure) and [HIr(depe)₂Cl]⁺[CH(CN)₂]- (6). Reaction of 5 with CO₂yields quantitatively 4 under mild reaction conditions.

Originalsprache	Englisch
Seiten (von - bis)	2307-2313
Seitenumfang	7
Fachzeitschrift	Organometallics
Jahrgang	6
Ausgabenummer	11
DOIs	https://doi.org/10.1021/om00154a007
Publikationsstatus	Veröffentlicht - 1 Nov. 1987

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@article{b102a1a293fd4d6f8eb37552c2e02906,

title = "Iridium- and Rhodium-Initiated C-C Coupling of Carbon Dioxide with Malonodinitrile",

abstract = "Electron-rich complexes of iridium(I) and rhodium(I) react with activated alkanes such as malonodinitrile and carbon dioxide under C-C coupling to give compounds of the general formula [LnMXH]+[O2CCH(CN)2]- (L = PMe3, n = 4; L = dmpe or depe, n = 2; X = Cl, H; M = Ir, Rh). The influence of the different phosphorus ligands on the structures of the complexes is described. Compounds [Hlr-(depe)2Cl]+[O2CCH(CN)2]- (1) and [H2Ir(PMe3)4]+[02CCH(CN)2]- (4) have been characterized by X-ray structure analyses which both show the dicyanoacetate anions to be dimeric via hydrogen bonds in the crystal form. To study the reaction mechanism the complexes HIr(PMe3)4and [Ir(depe)2]Cl were reacted in the absence of carbon dioxide with malonodinitrile and yielded the C-H activated malonodinitrile anion complexes [H2Ir(PMe3)4]+[CH(CN)2]- (5) (X-ray structure determination confirms the supposed molecular structure) and [HIr(depe)2Cl]+[CH(CN)2]- (6). Reaction of 5 with CO2yields quantitatively 4 under mild reaction conditions.",

author = "Arno Behr and Eberhardt Herdtweck and Herrmann, {Wolfgang A.} and Wilhelm Keim and Walter Kipshagen",

year = "1987",

month = nov,

day = "1",

doi = "10.1021/om00154a007",

language = "English",

volume = "6",

pages = "2307--2313",

journal = "Organometallics",

issn = "0276-7333",

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TY - JOUR

T1 - Iridium- and Rhodium-Initiated C-C Coupling of Carbon Dioxide with Malonodinitrile

AU - Behr, Arno

AU - Herdtweck, Eberhardt

AU - Herrmann, Wolfgang A.

AU - Keim, Wilhelm

AU - Kipshagen, Walter

PY - 1987/11/1

Y1 - 1987/11/1

N2 - Electron-rich complexes of iridium(I) and rhodium(I) react with activated alkanes such as malonodinitrile and carbon dioxide under C-C coupling to give compounds of the general formula [LnMXH]+[O2CCH(CN)2]- (L = PMe3, n = 4; L = dmpe or depe, n = 2; X = Cl, H; M = Ir, Rh). The influence of the different phosphorus ligands on the structures of the complexes is described. Compounds [Hlr-(depe)2Cl]+[O2CCH(CN)2]- (1) and [H2Ir(PMe3)4]+[02CCH(CN)2]- (4) have been characterized by X-ray structure analyses which both show the dicyanoacetate anions to be dimeric via hydrogen bonds in the crystal form. To study the reaction mechanism the complexes HIr(PMe3)4and [Ir(depe)2]Cl were reacted in the absence of carbon dioxide with malonodinitrile and yielded the C-H activated malonodinitrile anion complexes [H2Ir(PMe3)4]+[CH(CN)2]- (5) (X-ray structure determination confirms the supposed molecular structure) and [HIr(depe)2Cl]+[CH(CN)2]- (6). Reaction of 5 with CO2yields quantitatively 4 under mild reaction conditions.

AB - Electron-rich complexes of iridium(I) and rhodium(I) react with activated alkanes such as malonodinitrile and carbon dioxide under C-C coupling to give compounds of the general formula [LnMXH]+[O2CCH(CN)2]- (L = PMe3, n = 4; L = dmpe or depe, n = 2; X = Cl, H; M = Ir, Rh). The influence of the different phosphorus ligands on the structures of the complexes is described. Compounds [Hlr-(depe)2Cl]+[O2CCH(CN)2]- (1) and [H2Ir(PMe3)4]+[02CCH(CN)2]- (4) have been characterized by X-ray structure analyses which both show the dicyanoacetate anions to be dimeric via hydrogen bonds in the crystal form. To study the reaction mechanism the complexes HIr(PMe3)4and [Ir(depe)2]Cl were reacted in the absence of carbon dioxide with malonodinitrile and yielded the C-H activated malonodinitrile anion complexes [H2Ir(PMe3)4]+[CH(CN)2]- (5) (X-ray structure determination confirms the supposed molecular structure) and [HIr(depe)2Cl]+[CH(CN)2]- (6). Reaction of 5 with CO2yields quantitatively 4 under mild reaction conditions.

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Iridium- and Rhodium-Initiated C-C Coupling of Carbon Dioxide with Malonodinitrile

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