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首页> 外文期刊>Organometallics >Electronic and Magnetic Couplings in Free and pi-Coordinated 1,4-Diethynylnaphthalene-Bridged [Cp*(dppe)Fe](n+) (n=0, 1) Units
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Electronic and Magnetic Couplings in Free and pi-Coordinated 1,4-Diethynylnaphthalene-Bridged [Cp*(dppe)Fe](n+) (n=0, 1) Units

机译：以自由和π配位的1,4-二乙炔基萘桥连的[Cp *（dppe）Fe]（n +）（n = 0，1）单位的电子和磁耦合

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Treatment of freshly made 1,4-diethynylnapthalene with Cp*(dppe)FeCl in the presence of either NaPF6 or NaBPh4 salts provides the new binuclear organoiron bis(vinylidenes) [Cp*(dppe)Fe=C=CH-1,4-nph-CH=C=Fe(dppe)Cp*][X](2) (X = BPh4, PF6, Nph = naphthalenediyl, Cp* = eta(5)-C5Me5, dppe = 1,2-bis(diphenylphosphino)ethane), 4H(2)[PF6](2) and 4H(2)[BPh4](2). The daughter bis(acetylide) complex 4 was obtained upon deprotonation of the vinylidene precursor 4H(2)[PF6](2) by an excess of potassium tert-butoxide (80%). The heterotrimetallic complex [{Cp*(dppe)Fe=C=CH}(2)-{mu-(eta(6)-1, 4-nph)RuCp*}][PF6](3) (5H(2)[PF6](3)) was obtained upon reaction of the bis(vinylidene) 4H(2)[PF6](2) with [Cp*Ru(CH3CN)(3)][PF6] (82%). The regiopure bisacetylide isomer [Cp*(dppe)FeC C-1,4-nph-(Ru Cp*)-C CFe(dppe)Cp*][PF6] (5B[PF6]) was isolated as a dark brown powder (61%). The IR, H-1, C-13, and P-31 NMR, cyclic voltammetry, Mossbauer, and UV-vis data were obtained for the bisiron(II) complexes 4 and 5B[PF6]. All these data and the X-ray crystal structure determined for 5B[PF6] reveal a strong metal-metal interaction across the bridge reinforced by the Cp*Ru+ arenophile. When reacted with 2 equiv of [(C5H5)(2)Fe][PF6], 4 and 5B[PF6] provided the stable bisiron(III) complexes 4[PF6](2) and 5B[PF6](3) (60-80%), while treatment of 4 and 5B[PF6] with 1 equiv of 4[PF6](2) and 5B[PF6](3), respectively, gave the mixed valence (MV) compounds 4[PF6] and 5B[PF6](2) (88-98%). All the iron(III) complexes can be isolated and stored at 20 degrees C. ESR spectroscopy and magnetization measurements established that strong super exchange interaction propagates through the 1,4-diethynylnaphthalene bridge (J = -517 cm(-1) for 4[PF6](2) and J = -889 cm(-1) for 5B[PF6](2)). UV-vis-NIR spectra were obtained for the MV complexes, showing that a photodriven metal-metal electron-transfer process takes place over ca. 12 angstrom with a reorganization energy of ca. 4250 and 4410 cm(-1) for 4[PF6] and 5B[PF6](2), respectively. According to the Robin and Day classification, both MV compounds constitute nice examples of strongly coupled class III organometallic MV compounds (H-AD = 2140 cm(-1) for 4[PF6] and 2230 cm(-1) for 5B[PF6](2)).
机译：在NaPF6或NaBPh4盐存在下，用Cp *（dppe）FeCl处理新鲜制备的1,4-二乙炔萘可提供新的双核有机铁双（亚乙烯基）[Cp *（dppe）Fe = C = CH-1,4- nph-CH = C = Fe（dppe）Cp *] [X]（2）（X = BPh4，PF6，Nph =萘二甲酰基，Cp * = eta（5）-C5Me5，dppe = 1,2-双（二苯基膦基）乙烷），4H（2）[PF6]（2）和4H（2）[BPh4]（2）。在亚乙烯基前体4H（2）[PF6]（2）被过量的叔丁醇钾（80％）脱质子化后，获得了子代双（乙炔）配合物4。杂三金属配合物[{Cp *（dppe）Fe = C = CH}（2）-{mu-（eta（6）-1，4-nph）RuCp *}] [PF6]（3）（5H（2）通过双（亚乙烯基）4H（2）[PF6]（2）与[Cp * Ru（CH3CN）（3）] [PF6]（82％）反应获得[PF6]（3））。分离出深纯粉末状的区域纯双乙炔异构体[Cp *（dppe）FeC C-1,4-nph-（Ru Cp *）-C CFe（dppe）Cp *] [PF6]（5B [PF6]）（ 61％）。获得了双铁（II）配合物4和5B [PF6]的IR，H-1，C-13和P-31 NMR，循环伏安法，Mossbauer和UV-vis数据。所有这些数据和针对5B [PF6]确定的X射线晶体结构均显示出跨过Cp * Ru +亲油颗粒增强的桥的强烈金属-金属相互作用。当与2当量的[（C5H5）（2）Fe] [PF6]，4和5B [PF6]反应时，可得到稳定的双铁（III）配合物4 [PF6]（2）和5B [PF6]（3）（60 -80％），同时分别用1当量的4 [PF6]（2）和5B [PF6]（3）处理4和5B [PF6]，得到混合价（MV）化合物4 [PF6]和5B [PF6]（2）（88-98％）。所有的铁（III）配合物都可以分离并储存在20摄氏度下。ESR光谱和磁化强度测量表明，强的超级交​​换相互作用通过1,4-二乙炔基萘桥（J = -517 cm（-1）传播4 [ PF6]（2），对于5B [PF6]（2），J = -889 cm（-1）。获得了MV配合物的UV-vis-NIR光谱，表明光驱动的金属-金属电子转移过程发生在大约2,000℃。 12埃，重组能量为。 4 [PF6]和5B [PF6]（2）分别为4250和4410 cm（-1）。根据Robin和Day分类法，这两种MV化合物都是强耦合的III类有机金属MV化合物的很好的例子（4 [PF6]的H-AD = 2140 cm（-1），5B [PF6]的2230 cm（-1） （2））。

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