Synthesis, Structure, and Reactivity of Organochalcogen (Se, Te) Compounds Derived from 1-(N,N-Dimethylamino)naphthalene and N,N-Dimethylbenzylamine Arunashree Panda, † G. Mugesh, † Harkesh B. Singh,* ,† and Ray J. Butcher ‡ Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076 India, and Department of Chemistry, Howard University, Washington, D.C. 20059 Received October 5, 1998 A series of intramolecularly coordinated organochalcogen compounds incorporating the 8-(dimethylamino)-1-naphthyl and 2-[(dimethylamino)methyl]phenyl groups has been syn- thesized. All the compounds were synthesized using the ortholithiation methodology. Insertion of elemental selenium into the Li-C bond of RLi (6) (R ) 8-(dimethylamino)-1- naphthyl) afforded the lithium areneselenolate RSeLi (7). Oxidative workup of 7 yielded the yellow diselenide 8 in good yield. Reaction of 8 with a stoichiometric amount of sulfuryl chloride gave the monochloro derivative (9). Controlled bromination of diselenide (8) with bromine in carbon tetrachloride gave the stable selenenyl bromide (10). Compound 8 underwent facile reaction with a stoichiometric amount of iodine to give the corresponding novel monoiodo compound (11) in which selenium is covalently bonded to iodine. Attempts to synthesize the chalcogenides, R 2 E, 12 (E ) Se) and 13 (E ) Te), by the reaction of 6 with Se(dtc) 2 and Te(dtc) 2 (dtc ) diethyldithiacarbamate), respectively, were unsuccessful. The reaction of 6 with Te(dtc) 2 afforded the stable RTe(dtc) (14) instead of the expected telluride R 2 Te (13). In contrast, the reaction of R′Li (17) (R′ ) 2-[(dimethylamino)methyl)phenyl] with Se(dtc) 2 and Te(dtc) 2 afforded the expected selenide R′ 2 Se (18) and telluride R′ 2 Te (19), respectively, in moderate yields. The compounds were characterized by elemental analysis, NMR ( 1 H, 13 C, 77 Se, 125 Te), and mass spectral techniques. The structures of the compounds 9, 11, 14, and 18 were determined by X-ray crystallography. Although N‚‚‚E (E ) Se or Te) nonbonded interactions are present in the solid state in all the derivatives, in solution the pyramidal inversion at the nitrogen center is not blocked, and as a result, the NMe 2 signals are observed as sharp signals in the 1 H NMR spectra. Introduction Organochalcogens having an intramolecular E‚‚‚N interaction (E ) Se, Te) have attracted considerable current interest. In particular, the organoselenium derivatives find applications as (a) electrophilic and nucleophilic reagents in asymmetric synthesis where the intramolecular Se‚‚‚N interactions induce confor- mational rigidity in the molecule and these interactions are assumed to play a determinant role in chirality transfer, 1 (b) ligands in achiral and chiral catalysis, 2 (c) ligands for the isolation of monomeric and stable precursors for MOCVD of semiconductors, 3 (d) hyper- coordinated derivatives, 4 and (e) synthetic models for glutathione peroxidase where the Se‚‚‚N interactions play a key role in stabilizing the key intermediate selenenic acid. 5 † Indian Institute of Technology. ‡ Howard University. (1) (a) Wirth, T.; Fragale, G. Chem. Eur. J. 1997, 3, 1894. (b) Wirth, T. Liebigs Ann./Recl. 1997, 2189. (c) Wirth, T.; Fragale, G.; Spichty, M. J. Am. Chem. Soc. 1998, 120, 3376. (d) Fukuzawa, S.; Takahashi, K.; Kato, H.; Yamazaki, H. J. Org. Chem. 1997, 62, 7711, and references therein. (e) Fujita, K.; Murata, K.; Iwaoka, M.; Tomoda, S. Tetrahedron 1997, 53, 2029, and references therein. (f) Nishibayashi, Y.; Singh, J. D.; Fukuzawa, S.; Uemura, S. J. Org. Chem. 1995, 60, 4114. (g) Nishibayashi, Y.; Singh, J. D.; Fukuzawa, S.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 1995, 2871. (h) Nishibayashi, Y.; Segawa, K.; Singh, J. D.; Fukuzawa, S.; Ohe, K.; Uemura, S. Organometallics 1996, 15, 370, and references therein. (2) (a) Iwaoka, M.; Tomoda, S. J. Chem. Soc., Chem. Commun. 1992, 1165. (b) Wirth, T.; Hauptli, S.; Leuenberger, M. Tetrahedron: Asymm. 1998, 9, 547. (c) Kaur, R.; Singh, H. B.; Patel, R. P. J. Chem. Soc., Dalton Trans. 1996, 2719. (d) Fujita, K. Rev. Heteroatom. Chem. 1997, 16, 101. (3) (a) Cheng. Y.; Emge, T. J.; Brennan, J. G. Inorg. Chem. 1994, 33, 3711. (b) Cheng. Y.; Emge, T. J.; Brennan, J. G. Inorg. Chem. 1996, 35, 3342. (c) Cheng. Y.; Emge, T. J.; Brennan, J. G. Inorg. Chem. 1996, 35, 7339. (d) Kaur, R.; Singh, H. B.; Patel, R. P.; Kulshreshta, S. K. J. Chem. Soc., Dalton Trans. 1996, 461. (e) Mugesh, G.; Singh, H. B.; Patel, R. P.; Butcher, R. J. Inorg. Chem. 1998, 37, 2663. (4) (a) Fujihara, H.; Mima, H.; Furukawa, N. J. Am. Chem. Soc. 1995, 117, 10153. (b) Fujihara, H.; Mima, H.; Erata, T.; Furukawa, N. J. Chem. Soc., Chem. Commun. 1991, 98. (c) Fujihara, H.; Uehara, T.; Furukawa, N. J. Am. Chem. Soc. 1995, 117, 6388. (d) Fujihara, H.; Tanaka, H.; Furukawa, N. J. Chem. Soc., Perkin Trans. 2 1995, 2375. (e) Iwaoka, M.; Tomoda, S. J. Am. Chem. Soc. 1996, 118, 8077. (f) Iwaoka, M.; Tomoda, S. J. Org. Chem. 1995, 60, 5299. (5) (a) Wilson, S. R.; Zucker, P. A.; Huang, R.-R. C.; Spector, A. J. Am. Chem. Soc. 1989, 111, 5936. (b) Spector, A.; Wilson, S. R.; Zucker, P. A. US 5,321,138 (C1.546-224; C07C37/02), 1994 [Chem. Abst. 1994, 121, P 256039r]. (c) Engman, L.; Stern, D.; Cotgreave, I. A.; Andersson, C. M. J. Am. Chem. Soc. 1992, 114, 9737. (d) Iwaoka, M.; Tomoda, S. J. Am. Chem. Soc. 1994, 116, 2557. (e) Galet, V.; Bernier, J.-L.; Henichart, J.-P.; Lesieur, D.; Abadie, C.; Rochette, L.; Lindenbaum, A.; Chalas, J.; Faverie, J.-F. R.; Pfeiffer, B.; Renard, P. J. Med. Chem. 1994, 37, 2903. (f) Saiki, T.; Goto, K.; Okazaki, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 2223. 1986 Organometallics 1999, 18, 1986-1993 10.1021/om9808312 CCC: $18.00 © 1999 American Chemical Society Publication on Web 04/21/1999