Functionalization of the μ-Silylene Ligand in Cp2Fe2(CO)3(μ-SiHtBu): Syntheses of μ-Halosilylene Complexes Cp2Fe2(CO)3(μ-SiX'Bu) (X = Cl, Br, I) and Donor-Stabilized Cationic jn-Silylyne Complexes [Cp2Fe2(CO)3(μ-SitBu.Base)]I (Base = N-Methylimidazole, 4-(Dimethylamino)pyridine)

Yasuro Kawano, Hiromi Tobita, Mamoru Shimoi, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

Abstract

The μ-silylene complex Cp2Fe2(CO)3(M-SiHtBu) (1) reacts with CCl4, CHBr3, and CH2I2 at room temperature to afford μ-halosilylene complexes Cp2Fe2(CO)3(M-SiXtBu) (2, X = Cl; 3, X = Br; 4, X = I, respectively). The iodine atom on the silylene bridge in 4 is replaced by strong Lewis bases, N-methylimidazole (NMI) and 4-(dimethylamino)-pyridine (DMAP), to give the first donor-stabilized μ-silylyne dinuclear complexes [Cp2Fe2(CO)3(μ-SitBu·Base)]+ ([7]+, base = NMI; [8]+, Base = DMAP). The crystal structures of [7]I·CD3CN and [8]I have been determined by X-ray crystallography. Crystals of [7]I·CD3CN are orthorhombic, Pbnm, a = 16.371(4) Å, b = 17.043(3) Å, c = 9.975(1) Å, Z = 4, and R = 0.056. Crystals of [8]I are orthorhombic, Pbnm, a = 14.564(2) Å, b = 18.412(4) Å, c = 10.290(1) Å, Z = 4, and R = 0.070. These compounds have short Fe-Si bond lengths 2.262(2) Å ([7]I-CD3CN) and 2.266(3) Å ([8]I). In contrast, Si-N distances ([7]I.CD3CN, 1.885(7) Å; [8] 1,1.866(9) Å) are considerably longer than typical Si-N single bonds (ca. 1.75 Å), which is consistent with dative interaction between the nitrogen and silicon atoms. Spectroscopic properties of 2-[8]+ are also discussed.

Original languageEnglish
Pages (from-to)8575-8581
Number of pages7
JournalJournal of the American Chemical Society
Volume116
Issue number19
DOIs
Publication statusPublished - 1994 Sep 1

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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