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A Novel, Mercury-Free Synthetic Pathway for Trifluoromethylthio-Subsituted Metallocenes


Hess, Jeannine; Konatschnig, Sandro; Morard, Sanda; Pierroz, Vanessa; Ferrari, Stefano; Spingler, Bernhard; Gasser, Gilles (2014). A Novel, Mercury-Free Synthetic Pathway for Trifluoromethylthio-Subsituted Metallocenes. Inorganic Chemistry, 53(7):3662-3667.

Abstract

A novel synthetic pathway for trifluoromethylthioferrocene (3), which does not involve the use of toxic mercury(II)-based reagents, is described. The novel approach involves first the treatment of the commercially available bromoferrocene (1a) with NaSCN in the presence of copper(+I) to yield thiocyanatoferrocene (1), and then the reaction of 1 with the Rupper-Prakash reagent and tetrabutylammonium fluoride (TBAF) to give 3 in an overall yield of 60%. This approach could be extended for the preparation of thiocyanato-(4) and trifluoromethylthio-ruthenocene (7), which are herein both reported for the first time. Interestingly, diferrocenyl disulfide (2a) and diruthenocenyl disulfide (5) could be isolated as side-products during the synthesis of 3 and 7, respectively. All new compounds were unambiguously characterized by (1)H, (13)C, and (19)F NMR spectroscopy, mass spectrometry, cyclic voltammetry, elemental analysis, as well by X-ray crystallography for 1, 4, 4b, 5, 6, and 7. 1-7 were further tested for their toxic activity on cervical cancer (HeLa) and noncancerous (MRC-5) cell lines. All organometallic compounds were found either to be nontoxic or to have a moderate toxicity toward the cell lines used in this study.

Abstract

A novel synthetic pathway for trifluoromethylthioferrocene (3), which does not involve the use of toxic mercury(II)-based reagents, is described. The novel approach involves first the treatment of the commercially available bromoferrocene (1a) with NaSCN in the presence of copper(+I) to yield thiocyanatoferrocene (1), and then the reaction of 1 with the Rupper-Prakash reagent and tetrabutylammonium fluoride (TBAF) to give 3 in an overall yield of 60%. This approach could be extended for the preparation of thiocyanato-(4) and trifluoromethylthio-ruthenocene (7), which are herein both reported for the first time. Interestingly, diferrocenyl disulfide (2a) and diruthenocenyl disulfide (5) could be isolated as side-products during the synthesis of 3 and 7, respectively. All new compounds were unambiguously characterized by (1)H, (13)C, and (19)F NMR spectroscopy, mass spectrometry, cyclic voltammetry, elemental analysis, as well by X-ray crystallography for 1, 4, 4b, 5, 6, and 7. 1-7 were further tested for their toxic activity on cervical cancer (HeLa) and noncancerous (MRC-5) cell lines. All organometallic compounds were found either to be nontoxic or to have a moderate toxicity toward the cell lines used in this study.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:04 Faculty of Medicine > Institute of Molecular Cancer Research
07 Faculty of Science > Institute of Molecular Cancer Research

07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2014
Deposited On:06 Nov 2014 15:44
Last Modified:08 Dec 2017 07:59
Publisher:American Chemical Society
ISSN:0020-1669
Additional Information:Copyright © American Chemical Society
Publisher DOI:https://doi.org/10.1021/ic403169z
PubMed ID:24670103

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