Formation of Substituted Ferracyclopentadiene Complexes by the Reaction of Alkynes with Protonated Diferra-μ-azaallylidene Complexes

Thomas E. Snead, Chad A. Mirkin*, Kuang Lieh Lu, Son Binh Nguyen, Wu Chang Feng, Heather L. Beckman, Gregory L. Geoffroy, Arnold L. Rheingold, Brian S. Haggerty

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

The dinuclear complexes [Fe2{μ-C(H)(CH=NHR′)|(CO)8] [BF4] (Rr = But, Ph), which possess protonated μ21-azaallylidene ligands and are derivatives of the parent methylene complex Fe2(μ-CH2)(CO)8, react with alkynes (R1C≡CR2) to give isomeric hydroxy-imino-ferracyclopentadiene complexes, Fe2(μ-CR1CR2C(OH)C|C(H)=NR′})(CO)6, and amino-ferracyclopentadiene complexes, Fe2(μ-CR1CR2CHC{N-(H)R′})(CO)6, with the distribution of products dependent on the alkyne employed. The former were also isolated as their BF3 adducts Fe2(μ-CR1CR2C (O-BF3) C {C(H)≡NHR′}) (CO)6, and two of these latter complexes have been crystallographically characterized. They have a typical ferracyclopentadlene (ferróle) ring with an iminium substituent (C(H)=NHR′) on the α-carbon of the ring, which is hydrogen-bonded though the nitrogen atom to the oxygen substituent on the β-carbon of the ferracyclopentadlene ring, which is in turn coordinated by the BF3 group. The BF3group can be removed by reaction with aqueous base to give the free hydroxy-imino-ferracyclopentadiene complexes. The amino-ferracyclopentadiene complex with R′ = But and R1 = R2 = Ph has also been crystallographically characterized. It is a typical ferracyclopentadlene complex with an amino group on the α-carbon. The amino-ferracyclopentadiene complexes are also formed in near quantitative yield by an acid-catalyzed ring contraction of the 2-ferrapyridine complexes Fe2(μ-CR1CR2CHCHNR′) (CO)6.

Original languageEnglish (US)
Pages (from-to)2613-2622
Number of pages10
JournalOrganometallics
Volume11
Issue number7
DOIs
StatePublished - Jul 1 1992

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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