Nitrosyl derivatives of diiron(I) dithiolates mimic the structure and Lewis acidity of the [FeFe]-hydrogenase active site.
Nitrosyl derivatives of diiron(I) dithiolates mimic the structure and Lewis acidity of the [FeFe]-hydrogenase active site.
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二雄的硝基衍生物（I）二硫代酸盐模仿[FeFE] - 氢化酶活性位点的结构和刘易斯酸度。
DOI：
10.1021/ja802268p
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发表时间：
2008-09-10
影响因子：
15
通讯作者：
Wilson, Scott R.
中科院分区：
文献类型：
--
作者：
Olsen, Matthew T.;Bruschi, Maurizio;De Gioia, Luca;Rauchfuss, Thomas B.;Wilson, Scott R.
This study probes the impact of electronic asymmetry of diiron(I) dithiolato carbonyls. Treatment of Fe2(S2CnH2n)(CO)6-x(PMe3)x compounds (n = 2, 3) with NOBF4 gave the derivatives [Fe2(S2CnH2n)(CO)5-x(PMe3)x(NO)]BF4 (x = 1, 2, 3) which are electronically unsymmetrical due to the presence of a single NO+ ligand. Whereas the mono phosphine derivative is largely undistorted, the bis PMe3 derivatives are distorted such that the CO ligand on the Fe(CO)(PMe3)(NO)+ subunit is semibridging. Two isomers of [Fe2(S2C3H6)(CO)3(PMe3)2(NO)]BF4 were characterized spectroscopically and crystallographically. Each isomer features electron-rich [Fe(CO)2PMe3] and electrophilic [Fe(CO)(PMe3)(NO)]+ subunits. These species are in equilibrium with an unobserved isomer that reversibly binds CO (ΔH = −35 kJ/mol, ΔS = −139 J/mol•K) to give the symmetrical adduct [Fe2(S2C3H6)(μ-NO)(CO)4(PMe3)2]BF4. In contrast to Fe2(S2C3H6)(CO)4(PMe3)2, the bis(PMe3) nitrosyls readily undergo CO-substitution to give the (PMe3)3 derivatives. The nitrosyl complexes reduce at potentials that are ~1 V milder than their carbonyl counterparts. DFT calculations, specifically NBO values, reinforce the electronic resemblance of the nitrosyl complexes with the corresponding mixed-valence diiron complexes. Unlike other diiron dithiolato carbonyls, these species undergo reversible reductions at mild conditions. The results show that the novel structural and chemical features associated with mixed valence diiron dithiolates – the so-called Hox models - can be replicated in the absence of mixed-valency by introducing electronic asymmetry.
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影响因子：
4
作者：
Adam, Fatima I.;Hogarth, Graeme;Sanchez, Benjamin E.
通讯作者：
Sanchez, Benjamin E.
影响因子：
15
作者：
Boyke, CA;Rauchfuss, TB;Bénard, M
通讯作者：
Bénard, M
影响因子：
4.6
作者：
CRABTREE, RH;LAVIN, M
通讯作者：
LAVIN, M
影响因子：
15
作者：
Borg, SJ;Behrsing, T;Pickett, CJ
通讯作者：
Pickett, CJ
影响因子：
4.6
作者：
ADAMS, RD;COTTON, FA;MIHICHUK, L
通讯作者：
MIHICHUK, L