Trigonal-lantern dinuclear compounds of diiron(I,II): The synthesis and characterization of two highly paramagnetic Fe-2(amidinato)(3) species with short metal-metal bonds .1.
Trigonal-lantern dinuclear compounds of diiron(I,II): The synthesis and characterization of two highly paramagnetic Fe-2(amidinato)(3) species with short metal-metal bonds .1.
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DOI：
10.1016/s0020-1693(96)05469-2
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发表时间：
1997-03-31
影响因子：
2.8
通讯作者：
Murillo, CA
中科院分区：
文献类型：
--
作者：
Cotton, FA;Daniels, LM;Murillo, CA
FeCl2(HDPhF)(2) （HDPhF=N，N'-二苯基甲脒）和FeCl2(HDPhBz)(2) （HDPhBz=N，N'-二苯基甲脒）与NaEt3BH和甲基锂在四氢呋喃中反应形成了一种新型三角灯化合物，其中Fe-2（3+）单元由三个脒基团桥接。Fe-2(DPhF)(3) (I)晶体数据：单斜，空间群C2/c， a=17.154(4), b=8.255(1), c=23.400(5)埃，β =93.38(1)度，Z=4；Fe-2(DPhBz)(3)。2C(6)H(6) (II)：三角形，空间群c， a=11.237(2), c=76.510(7)埃，Z=6。化合物I和II的Fe-Fe键距分别为2.2318(8)和2.198(2)埃，是已知的二铁化合物中最短的。I和II的室温磁化率分别为7.81和7.53 B.M.， I在甲苯玻璃（10 K）中的EPR谱显示两个信号，g值分别为1.99和7.94，这与轴对称环境中存在7个未配对电子相一致。
Two examples of a new type of trigonal-lantern compound in which a formal Fe-2(3+) unit is bridged by three amidinato groups are formed by reacting FeCl2(HDPhF)(2) (HDPhF=N,N'-diphenylformamidine) and FeCl2(HDPhBz)(2) (HDPhBz=N,N'-diphenylbenzamidine) with NaEt3BH and methyllithium in THF. The isolated crystalline products, Fe-2(amidinato)(3), have been structurally characterized by X-ray crystallography at -60 degrees C. Crystal data for Fe-2(DPhF)(3) (I): monoclinic, space group C2/c, a=17.154(4), b=8.255(1), c=23.400(5) Angstrom, beta=93.38(1)degrees, Z=4; and for Fe-2(DPhBz)(3) . 2C(6)H(6) (II): trigonal, space group c, a=11.237(2), c=76.510(7) Angstrom, Z=6. The Fe-Fe bond distances, 2.2318(8) and 2.198(2) Angstrom for compounds I and II, respectively, are the shortest known for any diiron compound. The room temperature magnetic susceptibilities of 7.81 and 7.53 B.M. for I and II and the EPR spectrum of I in a toluene glass (10 K) which shows two signals at g values of 1.99 and 7.94 are consistent with the presence of seven unpaired electrons in an axially symmetric environment.