pubs.acs.org/Organometallics Published on Web 08/19/2009 r 2009 American Chemical Society 4958 Organometallics 2009, 28, 4958–4963 DOI: 10.1021/om900508b Reactivities of Secondary Phosphine Selenides Cp(CO) 2 FeP(Se)(OR) 2 : Formation of a Diiodine Charge Transfer Adduct and Se-Methylation Ling-Song Chiou, † Ching-Shiang Fang, † Bijay Sarkar, † Ling-Kang Liu, ‡ Max K. Leong,* ,† and C. W. Liu* ,† † Department of Chemistry, National Dong Hwa University, Hualien, Taiwan 97401, and ‡ Institute of Chemistry, Academia Sinica, Taipei, Taiwan Received June 15, 2009 The organoiron-substituted phosphine selenides Cp(CO) 2 FeP(Se)(OR) 2 (R= i Pr (1a), n Pr (1b), Et (1c)) were synthesized. The metalloligands, capable of reacting as nucleophiles toward Me 3 OBF 4 , formed Se-methylated products (2a-c). Upon reaction with diiodine, they formed spokelike charge- transfer adducts (3a-c). Among them 1b, 2b, and 3a were structurally authenticated, and 3a was the first structurally characterized, charge-transfer spoke adduct of a secondary phosphine selenide with diiodine. Since Zingaro and Meyers reported their spectroscopic studies confirming the formation of 1:1 adducts of tertiary phosphine selenides (R 3 PdSe) with diiodine in 1962, 1 sur- prisingly there was no further progress on this chemistry until Godfrey reported the solid-state structures of R 3 PSeI 2 in 1997. 2 It was found that phosphine selenides can donate electron density toward the σ* antibonding orbital of di- iodine to form a charge-transfer (CT) adduct, 3 as confirmed by single-crystal X-ray crystallography, since d(I-I) values in these adducts are elongated compared to that in I 2 in the solid state. Godfrey 4a and du Mont 4b also reported a few T-shaped charge-transfer adducts with dibromine. In contrast, all the tertiary phosphine selenide-diiodine 1:1 CT adducts known are spokelike. 2,5 Although a search in the Cambridge Structure Database results in several CT adducts of tertiary phosphine sulfide with dihalogens and interhalogens, 1,6 there has been no report of a CT adduct involving a secondary phosphine chalcogenide 7 with halogens or inter- halogens until now. On the other hand, a few reports on Se-glycosylations with the formation of a PSe-C bond by the nucleophilic attack of a phosphoroselenium unit on glycosyl bromide/anhydride 8 or via isomerization of a P(dSe)C unit 9 are known, which are important due to their potential biological activities. 10 It should be noted that recently this group has reported that the organoiron phosphoroselenide [Cp(CO) 2 Fe(O i Pr) 2 PSe], which contains [P(O i Pr) 2 Se] - , a conjugate base of the typical secondary phosphine selenide R 2 P(H)Se, allows P to retain the þ3 formal oxidation number and displays a longer P-Se bond upon metal complexation, characteristic for a secondary phosphine chalcogenide. 11a Herein, we report the synthesis of the metalloligands Cp(CO) 2 Fe(OR) 2 PSe (1a-c) along with the first report of a diiodine charge-transfer adduct of a secondary phosphine selenide, Cp(CO) 2 Fe(OR) 2 PSeI 2 (3a-c). 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