The Structure of a Metal-Cyclobutenyl Complex,[(CH3)4C4C5H5]NiC5H5
The Structure of a Metal-Cyclobutenyl Complex,[(CH3)4C4C5H5]NiC5H5
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金属环丁烯基配合物[(CH3)4C4C5H5]NiC5H5的结构
DOI：
10.1021/ic50024a005
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发表时间：
1965
影响因子：
4.6
通讯作者：
L. F. Dahl
中科院分区：
文献类型：
--
作者：
W. Oberhansli;L. F. Dahl
C13 H17 N1 C5 H5的Criegee-Ludwig-King化合物的结构测定揭示了环丁烯基金属络合物的第一个已证实的例子。晶体在正交晶胞中含有四个分子式单元，对称性为P2 i2 i2 i（D24），尺寸为a= 11.66±0.03 A.，B= 11.77±0.03 A.，c= 11.41±0.03 A。最后的三维各向同性最小二乘细化产生的差异因子%= 7.8%和R2= 10.2%，970观察到的反射。该结构由大约C.，- m对称性，其中每个镍（II）共价键合到α-环戊二烯基阴离子和非平面的1，2，3，4-四甲基-1-ε-环戊二烯并-1 ′，3 ′-二烯环丁烯基阴离子上。后者通过环丁烯基环系统的烯丙基片段对称地与镍（II）配位。烯丙基碳和双环碳的平面基本上平行，镍（II）夹在它们之间。详细的几何形状的环和立体化学进行了讨论。
The structural determination of the Criegee-Ludwig-King compound of composition C13H17N1C5H5 has revealed the first proven example of a cyclobutenyl-metal complex. The crystals containfour formula units in an orthorhombic unit cell of symmetry P2i2i2i (D24) anddimensions a= 11.66±0.03 A., b= 11.77±0.03 A., c= 11.41±0.03 A. The final three-dimensional isotropic least-squares refinement has yielded discrepancy factors of%= 7.8% and R2= 10.2% for 970 observed reflections. The structure consists of discrete molecules of approximately C.,-m symmetry in which each nickel (II) is covalently bonded to a-cyclopentadienyl anion and a nonplanar l, 2, 3, 4-tetramethyl-l-evo-cyclopenta-l', 3'-dienecyclobutenyl anion. The latter is symmetrically coordinated to the nickel (II) via the allylic fragment of the cyclobutenyl ring system. The planes of the allylic carbons and the cyclopentadienyl ring carbons are essentially parallel with the nickel (II) sandwiched between them. The detailed geometries of the rings and resulting stereochemistry are discussed.