Stereoselective Alkyne Insertion into a Bridging Hydride at a Diiron Centre: cis-trans Isomerisation and Metallacycle Formation

DOI: 10.1039/DT9940003389

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3389 - 3396 (1994)

Update date:2022-08-02

Topics:

Authors:

Hogarth, Graeme

Lavender, Mark H.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9940003389

Addition of the activated alkyne dimethyl acetylenedicarboxylate (dmad) to 1 (dppm = Ph2PCH2PPh2) afforded the ?-η vinyl complex cis-(μ-PPh2)(μ-dppm)> 2.Crystallography showed that the insertion is stereoselectively cis, with the phosphorus-containing ligands also adopting a cis configuration.Ultraviolet irradiation of 2 resulted in slow conversion into a second isomer, trans-(μ-PPh2)(μ-dppm)> 3, which still retains the cis arrangement of phosphines as shown by 31P NMR spectroscopy.This transformation is reversible, 3 slowly converting back into 2 at room temperature, a process which is accelerated upon heating.At temperatures of >/= 80 deg C, 2 (and 3) was converted irreversibly into a third isomer (μ-PPh2)(μ-dppm)> 4, containing a metallacyclic ring by virtue of metal co-ordination of an ester carbonyl.X-Ray crystallography revealed a trans vinyl orientation and a trans disposition of the phosphorus-containing groups.

Full text of DOI:10.1039/DT9940003389

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:cis-[Fe2(CO)4(μ-C(CO2Me)=CH(CO2Me))(μ-PPh2)(μ-dppm)]

Cas No:162524-71-2

R&D Labs maybe for 162524-71-2

shanghai payne pharm co.,ltd.

Contact:+86-021-58123769

Address:No.780 of Cailun Road,Zhangjiang Hi-tech Park,Pudong,Shanghai
Wuhan Kemi-Works Chemical Co., Ltd

website:http://www.kemiworks.com

Contact:86-27-85736489

Address:Rm. 1503, No. 164, Jianghan North Rd., Wuhan, 430022 China
He Bei Shun Er Chemical Co., LTD.

Contact:86-0311-86996932/86860168

Address:No 18,North street
Shanghai Apeptide Co., Ltd.

website:http://www.apeptides.com/en/

Contact:+86-21-60871011

Address:No. 80 Chuanshan Shuyuan Steet,Pudong,Shanghai
Changzhou Anyi Biochem Co., Ltd.(expird)

Contact:+86-519-88836158

Address:no,51 caoda

Relevant to this article

5-alkyloxy-6-fluorobenzo[c][1,2,5]thiadiazole- and silafluorene-based D-A alternating conjugated polymers: Synthesis and application in polymer photovoltaic cells

Doi:10.1021/ma500417r
(2014)
Aromatic nitrogen mustard-based prodrugs: Activity, selectivity, and the mechanism of DNA cross-linking

Doi:10.1002/chem.201400090
(2014)
A highly efficient route to C-3 alkyl-substituted indoles via a metal-free transfer hydrogenation

Doi:10.1016/j.tetlet.2014.05.064
(2014)
Highly efficient and generalized asymmetric synthesis of quaternary stereogenic carbon-containing β-amino indanones/indanoles via Mannich-type additions between 1-indanones and N-tert-butanesulfinylketimines

Doi:10.1039/c4ob00489b
(2014)
A "hemilabile" palladium-carbon bond: Characterization and its implication in catalysis

Doi:10.1021/om5005435
(2014)
Formation of condensed 1 H-pyrrol-2-ylphosphonates and 1,2-dihydropyridin- 2-ylphosphonates via Kabachnik-fields reaction of acetylenic aldehydes and subsequent 5-exo-dig or 6-endo-dig cyclizations

Doi:10.1021/jo501011u
(2014)

Article Doi