Molybdenum(IV)-porphyrin derivatives: the oxo(5,10,15,20-tetra-p-tolylporphyrinato)molybdenum(IV), MoO(TTP), and the dichloro(5,10,15,20-tetra-p-tolylporphyrinato)molybdenum(IV), Mo(Cl)21(TTP). Syntheses and structures
Molybdenum(IV)-porphyrin derivatives: the oxo(5,10,15,20-tetra-p-tolylporphyrinato)molybdenum(IV), MoO(TTP), and the dichloro(5,10,15,20-tetra-p-tolylporphyrinato)molybdenum(IV), Mo(Cl)21(TTP). Syntheses and structures
复制标题
钼(IV)-卟啉衍生物：氧代(5,10,15,20-四对甲苯基卟啉)钼(IV)、MoO(TTP)和二氯(5,10,15,20-四对甲苯基)
DOI：
10.1021/ic50195a004
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发表时间：
1979
影响因子：
4.6
通讯作者：
R. Weiss
中科院分区：
文献类型：
--
作者：
T. Diebold;B. Chevrier;R. Weiss
在温和条件下，氯化氢气体与氧代钼卟啉配合物MoO（TTP）反应，得到相应的二氯钼配合物Mo（Cl）2（TTP），其中TTP为5，10，15，20-四对甲苯基卟啉的阴离子。用X-射线衍射技术测定了两种化合物的分子立体化学。晶体数据如下。化合物I：MoO（TTP），单斜晶系，空间群Pije，Z= 4，a= 17.420（6）n，B= 16.851（6）n，c= 15.734（5）n，c = 112.23（4）.化合物II：Mo（Cl）2（TTP），正交晶系，空间群Fddl，Z= 16，a= 45.159（9）k，B= 35.671（7）k，c= 11.199（3）k.化合物I的精制基于2859个观察到的数据;最终的差异指数为Rx= 0.069和R2= 0.084。钼原子由四个吡咯氮原子和顶端氧原子五配位。Mo-O键长为1.656（6）nm，平均Mo-N键长为2.110（6）nm。钼原子位于四个氮原子的平均平面外0.6389（8）k处，朝向氧原子。该卟啉具有五配位金属卟啉的微凸特征。根据1977年的观测数据对化合物II进行了修正，最终的偏差指数为R_（1/2）= 0.053，R_（2/2）= 0.063。钼原子由四个吡咯氮原子和两个氯原子六配位。Mo-N平均键长为2.074（6）×。两个氯原子相互反式地连接到卟啉上，
Reaction of gaseous hydrogen chloride with the oxomolybdenum (IV) porphyrin complex MoO (TTP) under mild conditions affords the corresponding dichloromolybdenum (IV) complex Mo (C1) 2 (TTP), where TTP is the dianion of 5, 10, 15, 20-tetra-p-tolylporphyrin. The molecular stereochemistry of both compoundshas been determined by X-ray diffraction techniques using counter data. Crystal data are as follows. Compound I: MoO (TTP), monoclinic, space group Pije, Z= 4, a= 17.420 (6) Á, b= 16.851 (6) Á, c= 15.734 (5) Á, ß= 112.23 (4). Compound II: Mo (C1) 2 (TTP), orthorhombic, space group Fddl, Z= 16, a= 45.159 (9) k, b= 35.671 (7) Á, c= 11.199 (3) Á. Refinement of compound I was based on 2859 observed data; the final discrepancy indices were Rx= 0.069 and R2= 0.084. The molybdenum atom is pentacoordinated by the four pyrrole nitrogen atoms and the apical oxygen atom. The Mo-0 bond length is 1.656 (6) Á and the average Mo-N bond distance is 2.110 (6) Á. The molybdenum atom lies 0.6389 (8) k out of the mean plane of the four nitrogen atoms toward the oxygen atom. The porphyrin shows a slight doming characteristic of five-coordinate metalloporphyrins. Refinement of compound II was based on 1977observed data; the final discrepancy indices were R¡= 0.053 and R2= 0.063. The molybdenum atom is hexacoordinated by the four pyrrole nitrogen atoms and two chlorine atoms. The average Mo-N bond length is 2.074 (6) Á. Thetwo chlorine atoms are mutually trans with regardto the porphyrin, and the