PREPARATION AND STRUCTURAL CHARACTERIZATION OF MO2CL4(OAC)2(PR3)2 COMPOUNDS (R = ME, ET) AND A COMPARATIVE-STUDY OF THE SINGLET-TRIPLET SEPARATION FOR MO2CL4(OAC)2(PET3)2 WITH THAT FOR MO2CL6(DPPM)2
PREPARATION AND STRUCTURAL CHARACTERIZATION OF MO2CL4(OAC)2(PR3)2 COMPOUNDS (R = ME, ET) AND A COMPARATIVE-STUDY OF THE SINGLET-TRIPLET SEPARATION FOR MO2CL4(OAC)2(PET3)2 WITH THAT FOR MO2CL6(DPPM)2
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DOI：
10.1021/ic00074a036
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发表时间：
1993-10-27
影响因子：
4.6
通讯作者：
CHEN, H
中科院分区：
文献类型：
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作者：
COTTON, FA;SU, JN;CHEN, H
合成了两个新的化合物Mo_2Cl_4（OAc）_2（PEt_3）_2（1）和Mo_2Cl_4（OAc）_2（PMe_3）_2（2）。通过X射线晶体学确定它们的结构，并记录化合物1的质子NMR光谱作为温度的函数，以评估其单重态-三重态能隙;发现其为1033 +/-5 cm-1。有趣的是，化合物1与Mo_2Cl_6（dppm）_2（1.2）_3相比，具有更短的Mo-Mo距离和更小的单重态-三重态能隙。对此原因进行了讨论。这些化合物的晶体学数据如下：1，正交晶系Pca 2（1），a = 7.494（0）埃，B = 15.863（3）埃，c = 22.622（2）埃，V = 2689（2）埃，Z = 4，R = 0.033，R（w）= 0.044; 2，单斜P2（1）/c，其中a = 6.616（2）埃，B = 10.308（2）埃，c = 16.593（2）埃，β = 91.19（1）度，V = 1131.4（7）埃3，Z = 2，R = 0.060，和R（w）= 0.076。
Two new compounds Mo2Cl4(OAc)2(PEt3)2 (1) and Mo2Cl4(OAc)2(PMe3)2 (2) have been synthesized and found to be paramagnetic. Their structures were determined by X-ray crystallography, and the proton NMR spectrum of compound 1 was recorded as a function of temperature in order to evaluate its singlet-triplet energy gap; this was found to be 1033 +/- 5 cm-1. It is interesting to find that compound 1, compared with Mo2Cl6(dppm)2(1.2) 3, has the shorter Mo-Mo distance but the smaller singlet-triplet energy gap. The reason for this is discussed. The crystallographic data for these compounds are as follows: 1, orthorhombic Pca2(1) with a = 7.494(0) angstrom, b = 15.863(3) angstrom, c = 22.622(2) angstrom, V = 2689(2) angstrom3, Z = 4, R = 0.033, and R(w) = 0.044; 2, monoclinic P2(1)/c with a = 6.616(2) angstrom, b = 10.308(2) angstrom, c = 16.593(2) angstrom, beta = 91.19(1)-degrees, V = 11 31.4(7) angstrom3, Z = 2, R = 0.060, and R(w) = 0.076.