Issue 17, 2015
From the journal:

Dalton Transactions

A thorium metallacyclopentadiene complex: a combined experimental and computational study†

Bo Fang,a   Guohua Hou,a   Guofu Zi,*a   De-Cai Fang*a  and  Marc D. Walter*b  

* Corresponding authors

a Department of Chemistry, Beijing Normal University, Beijing 100875, China
E-mail: gzi@bnu.edu.cn, dcfang@bnu.edu.cn
Fax: +86-10-58802075
Tel: +86-10-58806051

b Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany
E-mail: mwalter@tu-bs.de
Fax: +49-531-3915387
Tel: +49-531-3915312

Abstract

The synthesis, structure, and reactivity of a thorium metallacyclopentadiene were comprehensively studied. The reduction of (η5-C5Me5)2ThCl2 (1) with potassium graphite (KC8) in the presence of diphenylacetylene (PhC[triple bond, length as m-dash]CPh) yields the first thorium metallacyclopentadiene complex (η5-C5Me5)2Th(η2-C4Ph4) (2). Density functional theory (DFT) studies suggest that the 5f orbitals are involved in the bonding of the metallacyclopentadiene Th–(η2-C[double bond, length as m-dash]C–C[double bond, length as m-dash]C) moiety. Compared to the thorium metallacyclopropene, complex 2 shows a distinctively different reactivity towards diazoalkanes and organic azides such as Me3SiCHN2, 9-diazofluorene and p-tolylN3, leading to the formation of the six-membered hydrazido complexes (η5-C5Me5)2Th[N(N[double bond, length as m-dash]CHSiMe3)(C4Ph4)] (3) and (η5-C5Me5)2Th[N(N[double bond, length as m-dash]C(C12H8))(C4Ph4)] (4) and the seven-membered bis(triazenido) complex (η5-C5Me5)2Th[N(N[double bond, length as m-dash]N(p-tolyl))(C4Ph4)N(N[double bond, length as m-dash]N(p-tolyl))] (5), respectively.

Graphical abstract: A thorium metallacyclopentadiene complex: a combined experimental and computational study

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Article information

DOI
https://doi.org/10.1039/C5DT00838G
Article type
Paper
Submitted
28 Feb 2015
Accepted
23 Mar 2015
First published
23 Mar 2015
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2015,44, 7927-7934

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A thorium metallacyclopentadiene complex: a combined experimental and computational study

B. Fang, G. Hou, G. Zi, D. Fang and M. D. Walter, Dalton Trans., 2015, 44, 7927 DOI: 10.1039/C5DT00838G

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