THE REDUCTION OF [FE(CO)(2)L(2)X(2)](L=P(OME)(3),P(OIPR)(3), PET(3), X=BR, I) - FROM IRON(II) TO IRON(0) VIA STABLE IRON(I) INTERMEDIATES

被引:41
作者
KANDLER, H
GAUSS, C
BIDELL, W
ROSENBERGER, S
BURGI, T
EREMENKO, IL
VEGHINI, D
ORAMA, O
BURGER, P
BERKE, H
机构
[1] Anorganisch-Chemisches Institut, Universität Zürich, Zürich, CH-8057
关键词
D O I
10.1002/chem.19950010808
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reduction of [Fe(CO)(2)L(2)X(2)] (L = P(OMe)(3), X = Br (1 a), I (1 b); L = P(OiPr)(3), X = Br (2 a), I (2 b); L = PEt(3), X = Br (3 a), I (3 b)) with Zn in dioxane (1 a,b-2 a,b) or PhLi in ether (3 a,b) led to formation of the corresponding dicarbonyl(halo)bis(phosphorus donor)iron(I) complexes (L = P(OMe)(3), X = Br (4 a), I (4 b); L = P(OiPr)(3), X = Br (5 a), I (5 b); L = PEt(3), X = Br (6 a), I (6 b)). Slightly contaminated 5 a,b and pure 6 a,b were isolated as stable crystalline blue or blue-green complexes. Complexes 4 a,b were obtained, with only minor impurities, by comproportionation of 1 a,b and the dicarbonyl(halo)bis(trimethylphosphite)ferrate anions 7 a,b and characterized in THF solution. The comproportionation products 5 a,b-6 a,b were obtained in high yields by reaction of 2 a,b-3 a,b with the dinitrogen complexes 13-15. Further reduction of 4 a,b-6 a,b or exhaustive reduction of 1 a,b-3 a,b with sodium amalgam or tBuLi in THF afforded the nonisolable dicarbonyl (halo)bis(phosphorus donor)ferrate(0) anions (7 a,b-9 a,b). The latter were characterized by acidification with trifluoroacetic acid or acetic acid yielding stable dicarbonyl(halo) hydridobis (phosphorus donor)iron(II) complexes (L = P(OMe)(3), X = Br (10 a), I (10 b); L = P(OiPr)(3), X = Br (11 a), I(11 b); L = PEt(3), X = Br (12 a), I (12 b)). In the presence of N-2, 8 a was transformed into dinitrogen complex [Fe(CO)(2){P(OiPr)(3)}N-2(2)] (13). With 9 a,b the reaction led to formation of [Fe(CO)(2)(PEt(3))(2)N-2] (14) and [{Fe(CO)(2)(PEt(3))(2)}(2)(mu-N-2)] (15). In solution at low temperature (-90 to 0 degrees C). the dinitrogen complexes 14 and 15 are in equilibrium with each other. Complexes 13, 14, and 15 were characterized by IR, H-1, C-13, P-31, and N-15 NMR spectroscopy. The structures of 5 a, 6 b, 14, and 15 were determined by X-ray diffraction studies.
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页码:541 / 548
页数:8
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