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

Technical University of Munich

Research output: Contribution to journal › Article › peer-review

26 Scopus citations

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.

Original language	English
Pages (from-to)	2307-2313
Number of pages	7
Journal	Organometallics
Volume	6
Issue number	11
DOIs	https://doi.org/10.1021/om00154a007
State	Published - 1 Nov 1987

Access to Document

10.1021/om00154a007

Cite this

@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",

publisher = "American Chemical Society",

number = "11",

}

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.

UR - http://www.scopus.com/inward/record.url?scp=0000745817&partnerID=8YFLogxK

U2 - 10.1021/om00154a007

DO - 10.1021/om00154a007

M3 - Article

AN - SCOPUS:0000745817

SN - 0276-7333

VL - 6

SP - 2307

EP - 2313

JO - Organometallics

JF - Organometallics

IS - 11

ER -

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

Abstract

Access to Document

Other files and links

Fingerprint

Cite this