Reactions of diacetylene ligands with trinuclear clusters. 3. Cyclization of diynes with β-amino moieties on the metal core of [H2Os3(CO)10]

Sergey P. Tunik, Vassily D. Khripun, Irina A. Balova, Ebbe Nordlander, Matti Haukka, Tapani A. Pakkanen, Paul R. Raithby

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Reactions of [H2Os3(CO)10] with the substituted diynes R-C2-C2-R′ (1, R = Ph, R′ = CH2NHPh; 2, R = Ph, R′ = CH2NHCH2Ph; 3, R = R′ = CH2NHPh) afford the clusters [HOs3(CO)10(L)] (L = {μ-η12-PhCH2C(H)=C-C(H)=C-NPh} (4), {μ-η12-PhCH2C(H)=C-C(H)= C-NCH2Ph} (5), and {μ-η11-CH3CC=C-C(H)=C(H)-NPh} (6), which have been characterized by single-crystal X-ray diffraction analyses as well as by various spectroscopic methods. In clusters 4-6, the starting diynes 1-3 have been rearranged to form substituted pyrrolyl rings which bridge two osmium atoms in η12- (4, 5) or η11- (6) coordination modes depending on the nature of substituents in 1-3. A possible reaction pathway for the diyne cyclization reactions that yield 4-6 involves initial transfer of a hydride onto a coordinated diyne followed by a series of 1,3-shifts and subsequent nucleophilic attack of the nitrogen on the third carbon atom of the diyne system to afford the five-membered pyrrolyl ring. Cluster 6 and its previously characterized furanyl analogue [HOs3(CO)10{μ-η11-(OCH- CHCC)-C-CH3)}] (7) undergo facile thermal transformation accompanied by the loss of a CO ligand to give the clusters [HOs3(CO)933- CH3CC=C-C(H)=C(H)-NPh}] (8) and [HOs3(CO)933-(OCH=CHC= CCCH3)}] (9). In both 8 and 9, single-crystal X-ray analysis revealed the presence of pentagonal pyramid cluster cores containing three osmium and three carbon atoms.

Original languageEnglish
Pages (from-to)3854-3863
Number of pages10
JournalOrganometallics
Volume20
Issue number18
DOIs
Publication statusPublished - 3 Sep 2001

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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