ISSN:
1572-8862
Schlagwort(e):
Iron
;
ynamine
;
aminoalkyne
;
diyne
;
carben
;
C-C coupling
;
insertion
;
structure
Quelle:
Springer Online Journal Archives 1860-2000
Thema:
Maschinenbau
,
Physik
Notizen:
Abstract The diiron ynamine complex [Fe2(CO)7{μ-C(Ph)C(NEt2)}] (1) reacts with the diphenylbuta-1, 4-diyne, PhC≡C-C≡CPh, in refluxing hexane to yield three isomer complexes [Fe2(CO)6{C(Ph)C(NEt2)C(Ph)C(C2Ph}] (2a), [Fe2(CO)6{C(Ph)C(NEt2)C(C2Ph)C(Ph)}] (2b), and [Fe2(CO)6{NEt2)C(Ph)C(C2)C(Ph)}] (2c) All three compounds were identified by their1H NMR spectra. Compounds2a and2c were characterized by single crystal X-ray diffraction analyses. Crystal data: for2a: space group = P21/n,a = 17.873(1) Å,β = 18.388(6) Å,c = 9.429(3) Å β = 91.99(3)°,Z = 4.3751 reflections,R = 0.044; for2c: space group = P21/n,a = 40.58(2) å,b = 12.101(9) Å,c = 12.551(5) Å,β = 94.29(7)°,Z = 8.4723 reflection,R = 0.076. Complexes2a and2b result from a [2 + 2] cycloaddition between one of the C≡C triple bonds of the diyne ligand and the Fe≡C carbene bond, whereas2c results from insertion of one of the C≡C group into the bridging carbene. Addition of [Fe2(CO)9] on2a gave two major products, the tripledecker [Fe3(CO)8{C(Ph)C(NEt2)C(C2Ph)}], (3 and a tetrairon cluster [Fe4(CO)11{C(Ph)C(NEt2)C(Ph)C(C2Ph)}] (4). Both compounds were characterized by single crystal diffraction analyses. Crystal data: for3: space group = P21/n,a = 12.039(3) Å,b = 18.046(3) å,c = 15.270(2) Å,β = 90.11(2)°,Z = 4, 1430 reflections,R = 0.067; for4 space group = C2/c,a = 18.633(3) Å,b = 21.467(1)_Å,c = 20.742(2) Å,β = 115.03(8)°,Z = 8.992 reflections, R = 0.076. Complex4 is based on a “spiked” triangular cluster with the alkynyl triple bond attached inμ 3-parallel mode on the triangular grouping.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1007/BF01379056
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