The butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 and its oxidative cleavage to (tBu3SiO)2Cr(=N-N=CPh2)2 and (tBu3SiO)2Cr=N(2,6-Ph2-C6H3).
The butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 and its oxidative cleavage to (tBu3SiO)2Cr(=N-N=CPh2)2 and (tBu3SiO)2Cr=N(2,6-Ph2-C6H3).
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蝶形二聚体 [(tBu3SiO)Cr]2(mu-OSitBu3)2 及其氧化裂解为 (tBu3SiO)2Cr(=N-N=CPh2)2 和 (tBu3SiO)2Cr=N(2,6-Ph2-C6H3)。
DOI：
10.1021/ic051481w
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发表时间：
2006
影响因子：
4.6
通讯作者：
T. Cundari
中科院分区：
文献类型：
--
作者：
O. Sydora;David S. Kuiper;P. T. Wolczanski;E. Lobkovsky;Adriana Dinescu;T. Cundari
将CrCl2(THf)2与NaOSitBu3反应得到蝴蝶二聚体[(TBu3SiO)Cr]2(Mu-OSitBu3)2(1(2))，其d(CrCr值)为2.658(31)A，磁性表明其具有较强的反铁磁性耦合作用。用[(Ho)2Cr]2(MuOH)2(1‘(2))计算得到的低能1A1、3B1、5A1、7B1和9A1态的Boltzmann分布提供了Mu(Jeff)与T数据的合理拟合。1(2)与不同的L(L=4-甲基吡啶、对甲苯腈、tBuCN、tBuNC、PPh2CO和PMe3)切割生成(TBu3SiO)2CrL2(1-L2)。二聚体被Ph2CN2氧化生成(TBu3SiO)2Cr(N2CPh2)2(2)，RN3在23℃氧化生成(Silox)2Cr=NR(3-R)，生成大R(金刚烷基(Ad)，2，6-iPr2-C6H3，2，4，6-ME3-C6H2=MES，2，6-PH2-C6H3)和(TBu3SiO)2Cr2(=NR)2(4-R)。在计算(H3SiO)2Cr=nPh(3‘-Ph)的基础上，对1(2)、正方形平面1-(OCPh_2)_2、拟Td2和拟三角3-(2，6-Ph_2-C_6H_3)的S=1基态进行了X射线结构研究。
Treatment of CrCl2(THF)2 with NaOSitBu3 afforded the butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 (1(2)), whose d(CrCr) of 2.658(31) A and magnetism were indicative of strong antiferromagnetic coupling. A Boltzmann distribution of low-energy 1A1, 3B1, 5A1, 7B1, and 9A1 states obtained from calculations on [(HO)2Cr]2(muOH)2 (1'(2)) were used to provide a reasonable fit of the mu(eff) vs T data. Cleavage of 1(2) with various L (L = 4-picoline, p-tolunitrile, tBuCN, tBuNC, Ph2CO, and PMe3) generated (tBu3SiO)2CrL2 (1-L2). The dimer was oxidatively severed by Ph2CN2 to give (tBu3SiO)2Cr(N2CPh2)2 (2) and by RN3 at 23 degrees C to afford (silox)2Cr=NR (3-R) for bulky R (adamantyl (Ad), 2,6-iPr2-C6H3, 2,4,6-Me3-C6H2 = Mes, 2,6-Ph2-C6H3) and (tBu3SiO)2Cr(=NR)2 (4-R) for smaller substituents (R = 1-Naph, 2-Anth). X-ray structural studies were conducted on 1(2), square planar 1-(OCPh2)2, pseudo-Td 2 and pseudo-trigonal 3-(2,6-Ph2-C6H3), whose S = 1 ground state was discussed on the basis of calculations of (H3SiO)2Cr=NPh (3' '-Ph).