SYNTHESIS, REACTIVITY, AND STRUCTURAL CHARACTERIZATION OF THE DINUCLEAR ZIRCONOCENOPHANE COMPLEXES [SIME2(C5H4)2][(C5H5)ZR(MU-X)]2 (X = S, CL)
SYNTHESIS, REACTIVITY, AND STRUCTURAL CHARACTERIZATION OF THE DINUCLEAR ZIRCONOCENOPHANE COMPLEXES [SIME2(C5H4)2][(C5H5)ZR(MU-X)]2 (X = S, CL)
复制标题
DOI：
10.1021/om00038a026
复制
发表时间：
1992-02-01
期刊：
影响因子：
2.8
通讯作者：
PETERSEN, JL
中科院分区：
文献类型：
--
作者：
CACCIOLA, J;REDDY, KP;PETERSEN, JL
用元素硫处理[SiMe 2（C5 H4）2][CpZrH（mu-H）]2得到二硫桥双核Zr（IV）配合物[SiMe 2（C5 H4）2][CpZr（mu-S）]2（1）。 [SiMe 2（C5 H4）2]-[CpZrCl（mu-H）]2的室温光解伴随着H2的还原消除和相应的二氯桥连双核Zr（III）配合物[SiMe 2（C5 H4）2][CpZr（mu-Cl）]2的形成而进行（2）。 这些抗磁性的zirconocenophane化合物已通过H-1和C-13 NMR测量，电子光谱，元素分析和X-射线晶体学方法进行了表征。 1和2与各种刘易斯碱的反应性研究用于评估Zr-（μ-X）-Zr（X = S，Cl）桥对裂解的敏感性。 在20-130 ℃的温度范围内，没有观察到1与PMe 3，CNMe或吡啶的可检测反应，而将PMe 3或THF添加到2中伴随着形成双核顺磁性Zr（III）加合物，其已在溶液中通过EPR鉴定。 2与Ph_3P = O和CO_2反应时，氧原子被抽离，生成氧桥物种[SiMe_2（C_5H_4）_2]-[CpZrCl]_2（μ-O）。 化合物1和2均以P2（1）/c对称（Z = 4）的单斜晶格结晶，晶胞参数为a = 17.148（5）埃，B = 8.178（2）埃，c = 15.611（4）埃，β = 91.95（2）度和a = 17.126（2）埃，分别为B = 8.098（1）埃，c = 15.624（4）埃，β = 91.16（2）度。 在每种情况下，中心Zr 2（mu-X）2核心与Zr…Zr的原子间距在1和2中分别为3.5210（6）和3.3853（4）埃。
The treatment of [SiMe2(C5H4)2][CpZrH(mu-H)]2 with elemental sulfur affords the disulfido-bridged dinuclear Zr(IV) complex [SiMe2(C5H4)2][CpZr(mu-S)]2 (1). Ambient photolysis of [SiMe2(C5H4)2]-[CpZrCl(mu-H)]2 proceeds with the reductive elimination of H2 and the formation of the corresponding dichloro-bridged dinuclear Zr(III) complex [SiMe2(C5H4)2][CpZr(mu-Cl)]2 (2). These diamagnetic zirconocenophane compounds have been characterized by H-1 and C-13 NMR measurements, electronic spectroscopy, elemental analysis, and X-ray crystallographic methods. Reactivity studies of 1 and 2 with various Lewis bases were used to evaluate the susceptibility of the Zr-(mu-X)-Zr (X = S, Cl) bridges to cleavage. No detectable reaction of 1 with PMe3, CNMe, or pyridine is observed within the temperature range of 20-130-degrees-C, whereas the addition of PMe3 or THF to 2 is accompanied by the formation of dinuclear paramagnetic Zr(III) adducts, which have been identified in solution by EPR. The reactions of 2 with Ph3P = O and CO2 occur with O atom abstraction giving the oxo-bridged species [SiMe2(C5H4)2]-[CpZrCl]2(mu-O). Compounds 1 and 2 both crystallize in a monoclinic lattice of P2(1)/c symmetry (Z = 4) with unit cell parameters of a = 17.148 (5) angstrom, b = 8.178 (2) angstrom, c = 15.611 (4) angstrom, beta = 91.95 (2)-degrees and a = 17.126 (2) angstrom, b = 8.098 (1) angstrom, c = 15.624 (4) angstrom, beta = 91.16 (2)-degrees, respectively. In each case, the central Zr2(mu-X)2 core is nearly planar with the Zr...Zr interatomic separation being 3.5210 (6) and 3.3853 (4) angstrom in 1 and 2, respectively.