CRYSTAL-STRUCTURES OF (MEC5H4)4U2(MU-NR)2 - UNSYMMETRICAL BRIDGING, R = PH, AND SYMMETRICAL BRIDGING, R = SIME3, ORGANOIMIDE LIGANDS IN ORGANOACTINIDE COMPOUNDS
CRYSTAL-STRUCTURES OF (MEC5H4)4U2(MU-NR)2 - UNSYMMETRICAL BRIDGING, R = PH, AND SYMMETRICAL BRIDGING, R = SIME3, ORGANOIMIDE LIGANDS IN ORGANOACTINIDE COMPOUNDS
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DOI：
10.1021/ja00222a011
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发表时间：
1988-07-06
影响因子：
15
通讯作者：
ZALKIN, A
中科院分区：
文献类型：
--
作者：
BRENNAN, JG;ANDERSEN, RA;ZALKIN, A
本文报道了四价铀桥联配合物（MeC/sub 5/H/sub 4/）/sub 2/（...嗯..通过（MeC/sub 5/H/sub 4/）/sub 3/U/times/thf和（MeC/sub 5/H/sub 4/）/sub 3/UNR的价态歧化反应制备了（NR）/sub 2/。对R = Ph和SiMe/sub 3/的X射线晶体学研究表明，NPh基团不对称地桥接两个铀碎片，而NSiMe/sub 3/基团对称地桥接两个铀碎片。（MeC/sub 5/H/sub 4/）/sub 4/U/sub 2/（NPh）/sub 2/晶体为单斜晶系，P2/sub 1//n，a = 14.738（3）/埃/，B = 9.933（2）/埃/，c = 10.612（2）/埃/，n = 10.612（3）/埃/，n = 10.612（3）/埃/。beta.. = 102.11（2）/度/在23/度/C。对于Z = 2（二聚体），计算的密度为2.13 g/cm/sup 3/。通过全矩阵最小二乘法将结构精修至0.029的常规R因子（1600个数据，F/sup 2/ > 2sigma（F/sup 2/））。（MeC/sub 5/H/sub 4/）/sub 4/U/sub 2/（NSiMe/sub 3/）/sub 2/也是单斜晶系，P2/sub 1//n，a = 15.761（6）/埃/，B = 9.389（4）/埃/，c = 11.052（4）/埃/，beta.. = 101.36（3）/度/在23/度/C。对于Z = 2（二聚体），计算的密度为2.00 g/cm/sup 3/。通过全矩阵最小二乘法将结构精修至0.023的常规R因子（2544个数据，F/sup 2/ > 2sigma（F/sup 2/））。这两种配合物都是二聚体，其中两个（MeC/sub 5/H/sub 4/）/sub 2/U片段通过有机酰亚胺基团桥接，使得反转中心位于U/sub 2/N/sub 2/环的中心。在NPh配合物中，桥连U-N距离为2.156（8）和2.315（8）/埃/，在NSiMe/sub 3/配合物中，桥连U-N距离为2.217（4）和2.230（4）/埃/。参考文献22篇，图3幅，表5张。
The tetravalent uranium complexes with bridging ligands, (MeC/sub 5/H/sub 4/)/sub 2/(..mu..-NR)/sub 2/ have been prepared by the valence conproportionation reaction of (MeC/sub 5/H/sub 4/)/sub 3/U/times/thf and (MeC/sub 5/H/sub 4/)/sub 3/UNR. X-ray crystallographic study of R = Ph and SiMe/sub 3/ shows that the NPh group asymmetrically bridges the two uranium fragments, whereas the NSiMe/sub 3/ group symmetrically bridges the two uranium fragments. Crystals of (MeC/sub 5/H/sub 4/)/sub 4/U/sub 2/(NPh)/sub 2/ are monoclinic, P2/sub 1//n, with a = 14.738 (3) /Angstrom/, b = 9.933 (2) /Angstrom/, c = 10.612 (2) /Angstrom/, ..beta.. = 102.11 (2)/degrees/ at 23/degrees/C. For Z = 2 (dimers) the calculated density is 2.13 g/cm/sup 3/. The structure was refined by full-matrix least-squares to a conventional R factor of 0.029 (1600 data, F/sup 2/ > 2sigma(F/sup 2/)). Crystals of (MeC/sub 5/H/sub 4/)/sub 4/U/sub 2/(NSiMe/sub 3/)/sub 2/ also are monoclinic, P2/sub 1//n, with a = 15.761 (6) /Angstrom/, b = 9.389 (4) /Angstrom/, c = 11.052 (4) /Angstrom/, ..beta.. = 101.36 (3)/degrees/ at 23/degrees/C. For Z = 2 (dimers) the calculated density is 2.00 g/cm/sup 3/. The structure was refined by full-matrix least-squares to a conventional R factor of 0.023 (2544 data, F/sup 2/ > 2sigma(F/sup 2/)). Both complexes are dimers in which the two (MeC/sub 5/H/sub 4/)/sub 2/U fragments are bridged by the organoimide group so that an inversion center is located in the center of the U/sub 2/N/sub 2/ ring. The bridging U-N distances are 2.156 (8) and 2.315 (8) /Angstrom/ in the NPh complex and 2.217 (4) and 2.230 (4) /Angstrom/ in the NSiMe/sub 3/ complex. 22 references, 3 figures, 5 tables.