A combined experimental and theoretical study of dinitrosyl iron complexes containing chelating bis(diphenyl)phosphinoX (X = benzene, propane and ethylene): X-ray crystal structures and properties influenced by the presence or absence of π-bonds in chelat
A combined experimental and theoretical study of dinitrosyl iron complexes containing chelating bis(diphenyl)phosphinoX (X = benzene, propane and ethylene): X-ray crystal structures and properties influenced by the presence or absence of π-bonds in chelat
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含有螯合双（二苯基）膦 X（X = 苯、丙烷和乙烯）的二亚硝基铁配合物的综合实验和理论研究：X 射线晶体结构和性质受螯合剂中存在或不存在 α 键的影响
DOI：
10.1016/j.poly.2013.12.019
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发表时间：
2014
期刊：
影响因子：
2.6
通讯作者：
Li,Lijuan
中科院分区：
文献类型：
--
作者：
Holloway,LaurenR;Clough,AndrewJ;Li,JessicaY;Tao,EmilyL;Tao,Fu-Ming;Li,Lijuan
最近有关一氧化氮在人体内作用的发现激发了人们对过渡金属亚硝基络合物的浓厚兴趣。合成了一系列式为[(DPPX)Fe(NO)2]，{DPPX=1，2-二(二苯基膦)苯(1)，1，3-二(二苯基膦)丙烷(2)，顺-1，2-双(二苯基膦)乙烯(3)的二亚硝基铁络合物，并结合红外光谱、核磁共振、紫外可见光谱、X-射线结晶学和电化学技术对其进行了表征。红外光谱显示络合物1和3的红外光谱没有移动到1723和1674 cm−1的区域，而2的红外光谱没有移动到1708和1660 cm−1的区域，这表明配体2是一个更强的σ供体。X-射线单晶数据表明，1和3具有稀有的球状构象，而2具有吸引构象。对化合物1、2和3的循环伏安研究表明，化合物1、2和3有两个准可逆氧化反应，其1/2值分别为0.101和0.186 nV、0.121和0.184 nV、0.019和0.342 nV。与化合物1和3相比，化合物2的Δe值较大，这归因于两个磷原子之间缺乏π-键。用密度泛函理论对合成的化合物和模型化合物进行了理论计算，计算结果与实验数据吻合较好。计算出化合物1、2和3的HOMO-LUMO缺口分别为3.736、4.060和3.669 EV，这支持了化合物2比化合物1和3更强的回馈。
Recent discoveries involving the roles of nitric oxide in humans have stimulated intense interest in transition metal nitrosyl complexes. A series of dinitrosyl iron complexes with the formula [(DPPX)Fe(NO)2], {DPPX = 1,2-bis(diphenylphosphino)benzene (1), 1,3-bis(diphenylphosphino)propane (2), and cis-1,2-bis(diphenylphosphino)ethylene (3)} has been prepared and characterized through a combination of FT-IR, NMR, UV–Vis, X-ray crystallography, and electrochemical techniques. Infrared spectroscopy showed NO shifts to the region of 1723 and 1674 cm−1for complexes1and3, and 1708 and 1660 cm−1for2, indicating that ligand2acts as a stronger σ-donor. The X-ray crystallographic data showed that1and3possess the rarerepulsoconformation while2has theattractoconformation. CV studies on compounds1,2and3display two quasi-reversible oxidations with theE°1/2values at 0.101 and 0.186 V, 0.121 and 0.184 V, and 0.019 and 0.342 V, respectively. The larger ΔEvalue for compound2compared with that of1and3is attributed to the lack of π-bonds between the two phosphorus atoms. Theoretical calculations using density functional theory were carried out on the synthesized compounds and model compounds and the results are consistent with the experimental data. The calculated HOMO–LUMO gaps for compounds1,2and3are 3.736, 4.060, and 3.669 eV, respectively, which supports the stronger back-donation for compound2than that of compounds1and3.