Syntheses and characterizations of α-iminopyridine compounds (alkylNCHpy)2Fe(L/Xn), and an assessment of redox non-innocence
Syntheses and characterizations of α-iminopyridine compounds (alkylNCHpy)2Fe(L/Xn), and an assessment of redox non-innocence
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α-亚氨基吡啶化合物(烷基NCHpy)2Fe(L/Xn)的合成和表征以及氧化还原非无罪的评估
DOI：
10.1016/j.poly.2012.08.060
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发表时间：
2013
期刊：
影响因子：
2.6
通讯作者：
E. Lobkovsky
中科院分区：
文献类型：
--
作者：
Emily C. Volpe;P. T. Wolczanski;Jonathan M. Darmon;E. Lobkovsky
顺式-（Me 3 P）4FeMe 2与2当量的neoPeNCH（2-py）反应得到{κ-N，N′-neoPeNCH（2-pyridyl）} 2FeMe 2（2-P）。在neoPeNCH存在下用Na/Hg还原FeCl_2（2-吡啶基）或neoHexNCH（2-吡啶基）和L（H_2CCHCO_2Me，PhCCPh，PMe_3）的存在证明了{κ-N，N′-neoPeNCH（2-吡啶基）}2Fe（H2CCHCO2Me）（2-P），但{κ-N，N′-neoPeNCH（2-吡啶基）}2Fe（PhCCPh）（5-P）、{κ-N，N′-neoHexNCH（2-吡啶基）}2Fe（PhCCPh）（5-H）和{κ-N，N′-neoHexNCH（2-吡啶基）}2Fe（PMe 3）（6-H）均以良好的产率分离。膦配合物6-H可以用CH 3 I或CH 3 OTf烷基化，得到[{κ-N，N′-neoHexNCH（2-pyridyl）}2Fe（PMe 3）Me]+I-（7-H-I）或[{κ-N，N′-neoHexNCH（2-pyridyl）}2Fe（PMe 3）Me]+OTf-（7-H-OTf）。[{κ-N，N′-RNCH（2-pyridyl）}3Fe][OTf]2（R=neoPe，8-P-OTf;neoHex，8-H-OTf）配合物也由Fe（OTf）2制备以鉴定某些反应中的潜在副产物。测试化合物2-P和7-H-OTf的乙烯低聚活性，但没有结果。配合物2-P，5-H，6-H和7-H-OTf的结构特征和评估通过穆斯堡尔谱，5-H被证明具有氧化还原非无辜的炔配体，而6-H的α-烷基亚氨基吡啶配体被归类为自由基阴离子，使所有化合物可描述为Fe（II）。
Treatment of cis-(Me3P)4FeMe2with two equivneoPeNCH(2-py) afforded {κ-N,N′-neoPeNCH(2-pyridyl)}2FeMe2(2-P). Reductions of FeCl2with Na/Hg in the presence ofneoPeNCH(2-pyridyl) orneoHexNCH(2-pyridyl) and L (H2CCHCO2Me, PhCCPh, PMe3) gave tentative evidence of {κ-N,N′-neoPeNCH(2-pyridyl)}2Fe(H2CCHCO2Me) (2-P), but {κ-N,N′-neoPeNCH(2-pyridyl)}2Fe(PhCCPh) (5-P), {κ-N,N′-neoHexNCH(2-pyridyl)}2Fe(PhCCPh) (5-H), and {κ-N,N′-neoHexNCH(2-pyridyl)}2Fe(PMe3) (6-H) were all isolated in good yield. Phosphine complex 6-H could be alkylated with CH3I or CH3OTf to afford [{κ-N,N′-neoHexNCH(2-pyridyl)}2Fe(PMe3)Me]+I−(7-H-I) or [{κ-N,N′-neoHexNCH(2-pyridyl)}2Fe(PMe3)Me]+OTf−(7-H-OTf). [{κ-N,N′-RNCH(2-pyridyl)}3Fe][OTf]2(R=neoPe, 8-P-OTf;neoHex, 8-H-OTf) complexes were also prepared from Fe(OTf)2in order to identify potential byproducts in certain reactions. Compounds 2-P and 7-H-OTf were tested for ethylene oligomerization activity, to no avail. Complexes 2-P, 5-H, 6-H, and 7-H-OTf were structurally characterized and evaluated by Mössbauer spectroscopy, and 5-H was shown to possess a redox non-innocent alkyne ligand, while the α-alkyliminopyridine ligands of 6-H were classified as radical anions, rendering all compounds describable as Fe(II).
影响因子：
4.9
作者：
Howson, Suzanne E.;Allan, Laura E. N.;Scott, Peter
通讯作者：
Scott, Peter