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Issue 41, 2016
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Synthesis, reactivity, structures, and dynamic properties of gyroscope like iron complexes with dibridgehead diphosphine cages: pre- vs. post-metathesis substitutions as routes to adducts with neutral dipolar Fe(CO)(NO)(X) rotors

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Abstract

Three routes are explored to the title halide/cyanide complexes trans-Fe(CO)(NO)(X)(P((CH2)14)3P) (9c-X; X = Cl/Br/I/CN), the Fe(CO)(NO)(X) moieties of which can rotate within the diphosphine cages (ΔHS (kcal mol−1/eu−1) 5.9/−20.4 and 7.4/−23.9 for 9c-Cl and 9c-I from variable temperature 13C NMR spectra). First, reactions of the known cationic complex trans-[Fe(CO)2(NO)(P((CH2)14)3P)]+ BF4 and Bu4N+ X give 9c-Cl/-Br/-I/-CN (75–83%). Second, reactions of the acyclic complexes trans-Fe(CO)(NO)(X)(P((CH2)mCH[double bond, length as m-dash]CH2)3)2 and Grubbs’ catalyst afford the tris(cycloalkenes) trans-Fe(CO)(NO)(X)(P((CH2)mCH[double bond, length as m-dash]CH(CH2)m)3P) (m/X = 6/Cl,Br,I,CN, 7/Cl,Br, 8/Cl,Br) as mixtures of Z/E isomers (24–41%). Third, similar reactions of trans-[Fe(CO)2(NO)(P((CH2)mCH[double bond, length as m-dash]CH2)3)2]+ BF4 and Grubbs’ catalyst afford crude trans-[Fe(CO)2(NO)P((CH2)mCH[double bond, length as m-dash]CH(CH2)m)3P)]+ BF4 (m = 6, 8). However, the C[double bond, length as m-dash]C hydrogenations required to consummate routes 2 and 3 are problematic. Crystal structures of 9c-Cl/-Br/-CN are determined. Although the CO/NO/X ligands are disordered, the void space within the diphosphine cages is analyzed in terms of horizontal and vertical constraints upon Fe(CO)(NO)(X) rotation and the NMR data. The molecules pack in identical motifs with parallel P–Fe–P axes, and without intermolecular impediments to rotation in the solid state.

Graphical abstract: Synthesis, reactivity, structures, and dynamic properties of gyroscope like iron complexes with dibridgehead diphosphine cages: pre- vs. post-metathesis substitutions as routes to adducts with neutral dipolar Fe(CO)(NO)(X) rotors

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Publication details

The article was received on 17 Aug 2016, accepted on 26 Sep 2016 and first published on 10 Oct 2016


Article type: Paper
DOI: 10.1039/C6DT03258C
Dalton Trans., 2016,45, 16190-16204
  • Open access: Creative Commons BY-NC license
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    Synthesis, reactivity, structures, and dynamic properties of gyroscope like iron complexes with dibridgehead diphosphine cages: pre- vs. post-metathesis substitutions as routes to adducts with neutral dipolar Fe(CO)(NO)(X) rotors

    G. M. Lang, D. Skaper, F. Hampel and J. A. Gladysz, Dalton Trans., 2016, 45, 16190
    DOI: 10.1039/C6DT03258C

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