Dynamic 15N NMR studies of iron phosphine complexes containing coordinated dinitrogen
Dynamic 15N NMR studies of iron phosphine complexes containing coordinated dinitrogen
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DOI：
10.1002/mrc.1247
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发表时间：
2003-09-01
影响因子：
2
通讯作者：
Luck, IJ
中科院分区：
文献类型：
--
作者：
Field, LD;Hazari, N;Luck, IJ
用N-15（2）交换未标记的配位二氮，原位合成了N-15标记的反式[FeH（N-2）（PP）（2）]（+）[BPh 4]（-）（PP=dppe，depe，dmpe）和顺式[FeH（N-2）（PP 3）]（+）[BPh 4]（-）配合物。N-15 NMR化学位移和耦合常数的报告。的N-15光谱表现出不同的信号的金属结合和终端氮原子的协调N-2。N-15共振显示N-15，N-15耦合，以及P-31，N-15耦合和长程N-15，H-1耦合时，有一个金属结合的配体。自由和协调的双氮之间的交换进行了监测，通过N-15-标记的网站之间的磁化转移，使用反转-转移-恢复实验。通过磁化转移也监测了金属结合的和协调的N-2的末端氮原子之间的交换，这可以通过N-2解离或通过分子内过程进行。版权所有（C）2003约翰威利父子有限公司。
The N-15-labelled iron dinitrogen complexes trans-[FeH(N-2)(PP)(2)](+)[BPh4](-) (PP=dppe, depe, dmpe) and cis-[FeH(N-2)(PP3)](+)[BPh4](-) were prepared in situ by exchange of unlabelled coordinated dinitrogen with N-15(2). N-15 NMR chemical shifts and coupling constants are reported. The N-15 spectra exhibit separate signals for the metal-bound and terminal nitrogen atoms of the coordinated N-2. The N-15 resonances display N-15, N-15 coupling as well as P-31, N-15 coupling and long-range N-15,H-1 coupling when there is a metal-bound hydrido ligand. Exchange between free and coordinated dinitrogen was monitored by magnetization transfer between N-15-labelled sites using an inversion-transfer-recovery experiment. Exchange between the metal-bound and terminal nitrogen atoms of coordinated N-2 was also monitored by magnetization transfer and this could proceed by N-2 dissociation or by an intramolecular process. Copyright (C) 2003 John Wiley Sons, Ltd.