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. 2017 Feb 13;36(3):605-613.
doi: 10.1021/acs.organomet.6b00803. Epub 2017 Jan 17.

A Straightforward Access to Stable, 16 Valence-electron Phosphine-Stabilized Fe0 Olefin Complexes and their Reactivity

Benjamin Burcher  1 , Kevin J Sanders  2 , Ladislav Benda  2 , Guido Pintacuda  2 , Erwann Jeanneau  3 , Andreas A Danopoulos  4 , Pierre Braunstein  4 , Hélène Olivier-Bourbigou  1 , Pierre-Alain R Breuil  1
Affiliations

A Straightforward Access to Stable, 16 Valence-electron Phosphine-Stabilized Fe0 Olefin Complexes and their Reactivity

Benjamin Burcher et al. Organometallics. .

Abstract

The use of the dialkene divinyltetramethyldisiloxane (dvtms) allows easy access to the reactive 16 valence-electron complexes [Fe0(L-L)(dvtms)], (L-L) = dppe (1,2-bis(diphenylphosphino)ethane), (1), dppp (1,2-bis(diisopropylphosphino)propane), (2), pyNMeP(iPr)2 (N-(diisopropylphosphino)-N-methylpyridin-2-amine), (4), dipe (1,2-bis(diisopropylphosphino)ethane), (5), and [Fe0(L)2(dvtms)], L = PMe3, (3), by a mild reductive route using AlEt2(OEt) as reducing agent. In contrast, by the same methodology, the 18 valence-electron complexes [Fe0(L-L)2(ethylene)], (L-L) = dppm (1,2-bis(diphenylphosphino)methane), 6, (L-L) = dppa (1,2-bis(diphenylphosphino)amine) 7 or (L-L)=dppe, 8, were obtained, which do not contain dvtms. In addition, a combined DFT and solid-state paramagnetic NMR methodology is introduced for the structure determination of 5. A comparative study of the reactivity of 1,2,4-6 and 8 with 3-hexyne highlights emerging mechanistic implications for C-C coupling reactions using these complexes as catalysts.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1
Synthesis of complexes 1-5.
Figure 1
Figure 1
Thermal ellipsoid representation (at 50% probability) of complexes (from top to bottom) 1, 2, 3 and 4; H atoms are not shown for clarity. Selected bond lengths (Å) and angles (°): For 1: P1-Fe1-P2 84.75(3); P1-Fe1 2.302(10); P2-Fe1 2.316(10); C3-C4 1.419(5); C1-C2 1.409(5); for 2: P1-Fe1-P2 91.37(2); P1-Fe1 2.291(6); P2-Fe1 2.335(6); C3-C4 1.418(3); C1-C2 1.415(3); for 3: P1-Fe1-P1 99.76(2); P1-Fe1 2.299(4); C1-C2 1.423(2); for 4: P1-Fe1-N2 80.77(6); P1-Fe1 2.245(8); Fe1-N2 2.147(2); C1-C2 1.417(3); C3-C4 1.422(3).
Figure 2
Figure 2
(a) X-ray structure of 1 (H atoms not shown for clarity). (b) DFT-optimized structure of 5. (c) Visualization of positive (blue) and negative (red) isosurfaces of spin density distribution in 5 (for ±0.0002 a.u. isovalues). (d) 13C PNMR spectrum of 5. The two CH2 carbons and their signals are labeled with a circle and a square in panels (c-d).
Scheme 2
Scheme 2
Synthetic route to complexes 6-8.
Figure 3
Figure 3
Thermal ellipsoid representation (at 50% probability) of complex 7. H atoms are not shown for clarity. Selected bond length (Å) and angles (°): P2-Fe1-P4 71.70(2); P29-Fe1-P31 71.78(2); C57-C56 1.423(3); C56-Fe1 2.069(2); C57-Fe1 2.050(2); P4-Fe1 2.189(6); P2-Fe1 2.209(6); P31-Fe1 2.198(6); P29-Fe1 2.175(6).
Figure 4
Figure 4
Thermal ellipsoid representation (at 50% probability) of complex 8 (50% probability displacement ellipsoids). H atoms are not shown for clarity. Selected bond length (Å) and angles (°): P2-Fe1-P5 84.35(8); P33-Fe-P30 83.72(8); C59-C58 1.441(11); C59-Fe1 2.082(8); C58-Fe1 2.099(7); P5-Fe12.229(2); P2-Fe1 2.238(2); P33-Fe1 2.214(2); P30-Fe1 2.210(2).
Scheme 3
Scheme 3
Suggested mechanism for alkyne cyclo-trimerization.
Figure 5
Figure 5
Thermal ellipsoid representation (at 50% probability) of complex 9. H atoms are not shown for clarity. Selected bond length (Å) and angles (°): P11-Fe1-P2 86.76(5); P11-Fe1 2.1501(14); P2-Fe1 2.136(14); P30-Fe1 2.150(14); Fe1-C34 1.874(5); Fe1-C35 1.860(5); C34-C35 1.303(6).
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