Alkylation of Methylene- and Ylide-Bridged Binuclear Gold(III) Complexes

Hubert Schmidbaur; Christoph Hartmann; Jürgen Riede; Brigitte Huber; Gerhard Müller

doi:10.1021/om00139a023

Alkylation of Methylene- and Ylide-Bridged Binuclear Gold(III) Complexes

Hubert Schmidbaur, Christoph Hartmann, Jürgen Riede, Brigitte Huber, Gerhard Müller

Department of Chemistry

Technical University of Munich

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

24 Scopus citations

Abstract

A-Frame complexes of the type [R₂P(CH₂)₂]₂(AuX)₂CH₂, where R = CH₃ or C₆H₅ and X = Br or I (2a-c) obtained by CH₂X₂ addition to the parent ylide complexes, were alkylated through the reaction with organolithium compounds under carefully controlled conditions. The complexes [(CH₃)₂P(CH₂)₂]₂(Au-n-C₄H9)₂CH₂ (3a) and [(C₆H5)₂P(CH₂)2]2(AuCH₃)₂CH₂ (3b) could be isolated and fully characterized. A partially alkylated intermediate [(C₆H₅)₂P(CH₂)₂]₂(AuCH₃)(AuBr)CH₂ (5) was also separated from the reaction mixture. A single-crystal X-ray structure analysis of 3b·C₆H₅CH₃ confirmed the proposed A-frame constitution based on a boat conformation of the gold ylide heterocycle with the two gold(III) centers in a square-planar environment of four aliphatic carbon atoms (P1, a = 11.852 (2), b = 13.120 (2), c = 13.715 (1) Å; a = 119.98 (1), β = 97.50 (1), y = 102.71 (1)°; V = 1727.5 Å³; d_calcd = 1.839 g/cm³ for Z = 2; R_w = 0.053 for 332 refined parameters and 5038 observations with F_o≥4.0 σ(F_o)). Complexes of the composition [R₂P(CH₂)₂]₂Au₂(CH₃)₂ are observed as byproducts, but no structural details are available as yet. Thermal decomposition of 3a,b leads to clean reductive elimination of propane from 3b but gives a mixture of products from 3a. The ylide complexes are regenerated in the process.

Original language	English
Pages (from-to)	1652-1656
Number of pages	5
Journal	Organometallics
Volume	5
Issue number	8
DOIs	https://doi.org/10.1021/om00139a023
State	Published - 1986

Access to Document

10.1021/om00139a023

Cite this

@article{80e494960edd45f1b19b05129fd3b06a,

title = "Alkylation of Methylene- and Ylide-Bridged Binuclear Gold(III) Complexes",

abstract = "A-Frame complexes of the type [R2P(CH2)2]2(AuX)2CH2, where R = CH3 or C6H5 and X = Br or I (2a-c) obtained by CH2X2 addition to the parent ylide complexes, were alkylated through the reaction with organolithium compounds under carefully controlled conditions. The complexes [(CH3)2P(CH2)2]2(Au-n-C4H9)2CH2 (3a) and [(C6H5)2P(CH2)2]2(AuCH3)2CH2 (3b) could be isolated and fully characterized. A partially alkylated intermediate [(C6H5)2P(CH2)2]2(AuCH3)(AuBr)CH2 (5) was also separated from the reaction mixture. A single-crystal X-ray structure analysis of 3b·C6H5CH3 confirmed the proposed A-frame constitution based on a boat conformation of the gold ylide heterocycle with the two gold(III) centers in a square-planar environment of four aliphatic carbon atoms (P1, a = 11.852 (2), b = 13.120 (2), c = 13.715 (1) {\AA}; a = 119.98 (1), β = 97.50 (1), y = 102.71 (1)°; V = 1727.5 {\AA}3; dcalcd = 1.839 g/cm3 for Z = 2; Rw = 0.053 for 332 refined parameters and 5038 observations with Fo≥4.0 σ(Fo)). Complexes of the composition [R2P(CH2)2]2Au2(CH3)2 are observed as byproducts, but no structural details are available as yet. Thermal decomposition of 3a,b leads to clean reductive elimination of propane from 3b but gives a mixture of products from 3a. The ylide complexes are regenerated in the process.",

author = "Hubert Schmidbaur and Christoph Hartmann and J{\"u}rgen Riede and Brigitte Huber and Gerhard M{\"u}ller",

year = "1986",

doi = "10.1021/om00139a023",

language = "English",

volume = "5",

pages = "1652--1656",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Alkylation of Methylene- and Ylide-Bridged Binuclear Gold(III) Complexes

AU - Schmidbaur, Hubert

AU - Hartmann, Christoph

AU - Riede, Jürgen

AU - Huber, Brigitte

AU - Müller, Gerhard

PY - 1986

Y1 - 1986

N2 - A-Frame complexes of the type [R2P(CH2)2]2(AuX)2CH2, where R = CH3 or C6H5 and X = Br or I (2a-c) obtained by CH2X2 addition to the parent ylide complexes, were alkylated through the reaction with organolithium compounds under carefully controlled conditions. The complexes [(CH3)2P(CH2)2]2(Au-n-C4H9)2CH2 (3a) and [(C6H5)2P(CH2)2]2(AuCH3)2CH2 (3b) could be isolated and fully characterized. A partially alkylated intermediate [(C6H5)2P(CH2)2]2(AuCH3)(AuBr)CH2 (5) was also separated from the reaction mixture. A single-crystal X-ray structure analysis of 3b·C6H5CH3 confirmed the proposed A-frame constitution based on a boat conformation of the gold ylide heterocycle with the two gold(III) centers in a square-planar environment of four aliphatic carbon atoms (P1, a = 11.852 (2), b = 13.120 (2), c = 13.715 (1) Å; a = 119.98 (1), β = 97.50 (1), y = 102.71 (1)°; V = 1727.5 Å3; dcalcd = 1.839 g/cm3 for Z = 2; Rw = 0.053 for 332 refined parameters and 5038 observations with Fo≥4.0 σ(Fo)). Complexes of the composition [R2P(CH2)2]2Au2(CH3)2 are observed as byproducts, but no structural details are available as yet. Thermal decomposition of 3a,b leads to clean reductive elimination of propane from 3b but gives a mixture of products from 3a. The ylide complexes are regenerated in the process.

AB - A-Frame complexes of the type [R2P(CH2)2]2(AuX)2CH2, where R = CH3 or C6H5 and X = Br or I (2a-c) obtained by CH2X2 addition to the parent ylide complexes, were alkylated through the reaction with organolithium compounds under carefully controlled conditions. The complexes [(CH3)2P(CH2)2]2(Au-n-C4H9)2CH2 (3a) and [(C6H5)2P(CH2)2]2(AuCH3)2CH2 (3b) could be isolated and fully characterized. A partially alkylated intermediate [(C6H5)2P(CH2)2]2(AuCH3)(AuBr)CH2 (5) was also separated from the reaction mixture. A single-crystal X-ray structure analysis of 3b·C6H5CH3 confirmed the proposed A-frame constitution based on a boat conformation of the gold ylide heterocycle with the two gold(III) centers in a square-planar environment of four aliphatic carbon atoms (P1, a = 11.852 (2), b = 13.120 (2), c = 13.715 (1) Å; a = 119.98 (1), β = 97.50 (1), y = 102.71 (1)°; V = 1727.5 Å3; dcalcd = 1.839 g/cm3 for Z = 2; Rw = 0.053 for 332 refined parameters and 5038 observations with Fo≥4.0 σ(Fo)). Complexes of the composition [R2P(CH2)2]2Au2(CH3)2 are observed as byproducts, but no structural details are available as yet. Thermal decomposition of 3a,b leads to clean reductive elimination of propane from 3b but gives a mixture of products from 3a. The ylide complexes are regenerated in the process.

UR - http://www.scopus.com/inward/record.url?scp=10544254960&partnerID=8YFLogxK

U2 - 10.1021/om00139a023

DO - 10.1021/om00139a023

M3 - Article

AN - SCOPUS:10544254960

SN - 0276-7333

VL - 5

SP - 1652

EP - 1656

JO - Organometallics

JF - Organometallics

IS - 8

ER -

Alkylation of Methylene- and Ylide-Bridged Binuclear Gold(III) Complexes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this