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Chen Y, Peng Y, Chen P, Zhao J, Liu L, Li Y, Chen S, Qu J: Insertion reactions of CS2, COS, and PhNCS at thiolate-bridged diiron centers. Dalton Trans. 2010 Mar 28;39(12):3020-5. Epub 2009 Dec 23.
Treatment of [Cp*Fe (mu (2)-SR)(3) FeCp*] (1a, R = Et; 1b, R = Me) with CS (2) obtains the insertion products [Cp*Fe (mu (2)-SR)(2)(mu-eta (2)-S (2) CSR) FeCp*] (2a, R = Et; 2b, R = Me) with the retained Fe (2) S (2) subunit in excellent yield. 2a and 2b represent the first examples for the CS (2) activation and incorporation at the diiron-SR bond. [Cp*Fe (mu (2)-SEt)(2)(mu-eta (2)-S (2)) FeCp*] (3) is prepared from COS and 1a through the decarbonylation and sulfur coupling reaction of COS resulting in the formation of S (2)(2-) ligand. Addition of PhNCS into 1a affords a mononuclear complex [Cp*Fe (SEt)(eta (2)-SC (SEt) NPh)] (4). 1a is found to be unreactive towards CO (2). The spectral characterization, X-ray diffraction analysis, and electrochemistry of the insertion products have also been described. |
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