Issue 41, 2010
From the journal:

Dalton Transactions

Carbene–carbanion equilibrium for tris(2-pyridylthio)methanido Fe(ii) complexes†

Naoto Kuwamura,abc   Ryo Kato,a   Ken'ichi Kitano,a   Masakazu Hirotsu,ac   Takanori Nishioka,abc   Hideki Hashimotoabc  and  Isamu Kinoshita*abc  

* Corresponding authors

a Departments of Material Science and Physics, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka, Japan
E-mail: isamu@sci.osaka-cu.ac.jp
Fax: +816 6690 2753
Tel: +816 6605 2519

b CREST, Japan Science and Technology Agency, 4-1-8 Honcho Kawaguchi, Saitama, Japan

c The Osaka City University Advanced Research Institute for Natural Science and Technology, Osaka, Japan

Abstract

A reaction of FeCl2 with tris(2-pyridylthio)methane (tptmH) produced the carbanion complex [Fe(tptm)(CH3CN)2](FeCl4){(C2H5)3NH}. When FeI2 was used instead of FeCl2, the carbene complex [FeI(pyt)(bptmd)] (pyt = 2-pyridinethiolate, bptmd = bis(2-pyridylthio)methylidene) was isolated. The carbene forms [FeX(pyt)(bptmd)]n+ (n = 1 for X = CH3CN, n = 0 for X = I) were observed for [Fe(tptm)(CH3CN)2](FeCl4){(C2H5)3NH} and [FeI(pyt)(bptmd)] in chloroform, whereas the carbene–carbanion equilibrium was observed in acetonitrile by NMR measurements. The thermodynamic parameters were evaluated by variable temperature 1H NMR measurements using the diamagnetic salt [Fe(tptm)(CH3CN)2]PF6 for [Fe(tptm)(CH3CN)2]+ ⇆ [Fe(pyt)(bptmd)(CH3CN)]+ + CH3CN (ΔH = 23 kJ mol−1, ΔS = 55 J mol−1 K−1).

Graphical abstract: Carbene–carbanion equilibrium for tris(2-pyridylthio)methanido Fe(ii) complexes

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Article information

DOI
https://doi.org/10.1039/C0DT00615G
Article type
Paper
Submitted
07 Jun 2010
Accepted
02 Aug 2010
First published
21 Sep 2010

Dalton Trans., 2010,39, 9988-9993

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Carbene–carbanion equilibrium for tris(2-pyridylthio)methanido Fe(II) complexes

N. Kuwamura, R. Kato, K. Kitano, M. Hirotsu, T. Nishioka, H. Hashimoto and I. Kinoshita, Dalton Trans., 2010, 39, 9988 DOI: 10.1039/C0DT00615G

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