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Song LC, Fan HT, Hu QM, Yang ZY, Sun Y, Gong FH: Formation and chemical reactivities of a new type of double-butterfly [[Fe2 (mu-CO)(CO) 6] 2 (mu-SZS-mu)] 2-: synthetic and structural studies on novel linear and macrocyclic butterfly Fe/E (E=S, Se) cluster complexes. Chemistry. 2003 Jan 3;9(1):170-80.
A new type of double-butterfly [[Fe (2)(mu-CO)(CO)(6)](2)(mu-SZS-mu)](2-) (3), a dianion that has two mu-CO ligands, has been synthesized from dithiol HSZSH (Z=(CH (2))(4), CH (2)(CH (2) OCH (2))(1-3) CH (2)), [Fe (3)(CO)(12)], and Et (3) N in a molar ratio of 1:2:2 at room temperature. Interestingly, the in situ reactions of dianions 3 with various electrophiles affords a series of novel linear and macrocyclic butterfly Fe/E (E=S, Se) cluster complexes. For instance, while reactions of 3 with PhC (O) Cl and Ph (2) PCl give linear clusters [[Fe (2)(mu-PhCO)(CO)(6)](2)(mu-SZS-mu)] (4 a,b: Z=CH (2)(CH (2) OCH (2))(2,3) CH (2)) and [[Fe (2)(mu-Ph (2) P)(CO)(6)](2)(mu-SZS-mu)] (5 a,b: Z=CH (2)(CH (2) OCH (2))(2,3) CH (2)), reactions with CS (2) followed by treatment with monohalides RX or dihalides X-Y-X give both linear clusters [[Fe (2)(mu-RCS (2))(CO)(6)](2)(mu-SZS-mu)] (6 a-e: Z=CH (2)(CH (2) OCH (2))(1,2) CH (2); R=Me, PhCH (2), FeCp (CO)(2)) and macrocyclic clusters [[Fe (2)(CO)(6)](2)(mu-SZS-mu)(mu-CS (2) YCS (2)-mu)] (7 a-e: Z=(CH (2))(4), CH (2)(CH (2) OCH (2))(1-3) CH (2); Y=(CH (2))(2-4), 1,3,5-Me (CH (2))(2) C (6) H (3), 1,4-(CH (2))(2) C (6) H (4)). In addition, reactions of dianions 3 with [Fe (2)(mu-S (2))(CO)(6)] followed by treatment with RX or X-Y-X give linear clusters [[[Fe (2)(CO)(6)](2)(mu-RS)(mu (4)-S)](2)(mu-SZS-mu)] (8 a-c: Z=CH (2)(CH (2) OCH (2))(1,2) CH (2); R=Me, PhCH (2)) and macrocyclic clusters [[[Fe (2)(CO)(6)](2)(mu (4)-S)](2)(mu-SYS-mu)(mu-SZS-mu)] (9 a,b: Z=CH (2)(CH (2) OCH (2))(2,3) CH (2); Y=(CH (2))(4)), and reactions with SeCl (2) afford macrocycles [[Fe (2)(CO)(6)](2)(mu (4)-Se)(mu-SZS-mu)] (10 d: Z=CH (2)(CH (2) OCH (2))(3) CH (2)) and [[[Fe (2)(CO)(6)](2)(mu (4)-Se)](2)(mu-SZS-mu)(2)] (11 a-d: Z=(CH (2))(4), CH (2)(CH (2) OCH (2))(1-3) CH (2)). Production pathways have been suggested; these involve initial nucleophilic attacks by the Fe-centered dianions 3 at the corresponding electrophiles. All the products are new and have been characterized by combustion analysis and spectroscopy, and by X-ray diffraction techniques for 6 c, 7 d, 9 b, 10 d, and 11 c in particular. X-ray diffraction analyses revealed that the double-butterfly cluster core Fe (4) S (2) Se in 10 d is severely distorted in comparison to that in 11 c. In view of the Z chains in 10 a-c being shorter than the chain in 10 d, the double cluster core Fe (4) S (2) Se in 10 a-c would be expected to be even more severely distorted, a possible reason for why 10 a-c could not be formed. |
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