SYNTHESIS OF ETHYLENE, CYCLO-OCTA-1,5-DIENE, BICYCLO[2.2.1]HEPTENE, AND TRANS-CYCLO-OCTENE COMPLEXES OF PALLADIUM(0) AND PLATINUM(0) - CRYSTAL AND MOLECULAR-STRUCTURE OF "TRIS(BICYCLO[2.2.1]HEPTENE)PLATINUM
SYNTHESIS OF ETHYLENE, CYCLO-OCTA-1,5-DIENE, BICYCLO[2.2.1]HEPTENE, AND TRANS-CYCLO-OCTENE COMPLEXES OF PALLADIUM(0) AND PLATINUM(0) - CRYSTAL AND MOLECULAR-STRUCTURE OF "TRIS(BICYCLO[2.2.1]HEPTENE)PLATINUM
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DOI：
10.1039/dt9770000271
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发表时间：
1977-01-01
期刊：
影响因子：
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通讯作者：
STONE, FGA
中科院分区：
文献类型：
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作者：
GREEN, M;HOWARD, JAK;STONE, FGA
[Pt(1,5- c8h12)Cl2]与Li2（C8H8）在乙醚中过量的1,5- c8h12存在下反应，得到白色结晶配合物[Pt(1,5- c8h12)2]，产率高。在丙烯存在下，[Pd(1,5- c8h12)Cl2]的类似反应得到[Pd(1.5-C8H12)2]。在环境温度下稳定。[M(1,5- c8h12)Cl2]（M = Pd或Pt）与Li2（C8H8）和过量的双环[2.2.1]庚烯反应，分别得到三（双环[2.2.1]庚烯）-钯和-铂。这些配合物也可由双环[2.2.1]庚烯取代[M(1,5- c8h12)2]（M = Pd或Pt）中的环-八-1,5-二烯得到。与反环辛烯和乙烯的相关置换反应分别得到三（反环辛烯）钯和三（反环辛烯）铂。三（乙烯）钯和三（乙烯）铂。乙烯配合物极易挥发，虽然它们很容易沉积金属，但可以作为结晶物分离出来。利用四圆衍射仪在室温和190k下记录的单晶x射线数据，建立了三（双环-[2.2.1]庚烯）铂的结构同一性。该配合物为正交体，空间群P212121。Z = 4 = 5.717 (1), b = 10.735 (4), c = 28.749(12),在300 K:在190 K = 5.598 (6), b = 10.775 (16), c = 28.562(40)。使用1 781个反射的全矩阵最小二乘细化已收敛到R 0.056 (R ' 0.066)（190 K数据）。分子具有三角平面结构，其与平面度的最大偏差为0.03 Å。
Reaction of [Pt(1,5-C8H12)Cl2] with Li2(C8H8) in diethyl ether in the presence of excess of 1,5-C8H12 gives the white crystalline complex [Pt(1,5-C8H12)2] in good yield. A similar reaction of [Pd(1,5-C8H12)Cl2] in the presence of propene affords [Pd(1.5-C8H12)2]. stable below ambient temperatures. The reaction of [M(1,5-C8H12)Cl2](M = Pd or Pt) with Li2(C8H8) and excess of bicyclo[2.2.1]heptene gives, respectively, tris(bicyclo[2.2.1]heptene)- palladium and -platinum. These complexes are also obtained by displacement of cyclo-octa-1,5-diene from [M(1,5-C8H12)2](M = Pd or Pt) by bicyclo[2.2.1]heptene. Related displacement reactions with trans-cyclo-octene and ethylene afford, respectively, tris(trans-cyclo-octene)palladium, tris(trans-cyclo-octene)platinum. tris(ethylene)palladium, and tris(ethylene)platinum. The ethylene complexes are highly volatile, and can be isolated as crystalline species, although they readily deposit the metals. The structural identity of tris(bicyclo-[2.2.1]heptene)platinum has been established by analysis of single-crystal X-ray data recorded on a four-circle diffractometer both at room temperature and at 190 K. The complex is orthorhombic, space group P212121. Z= 4, a= 5.717(1), b= 10.735(4), c= 28.749(12)Å, at 300 K: at 190 K a= 5.598(6), b= 10.775(16), c= 28.562(40)Å. Full-matrix least-squares refinement, using 1 781 reflections, has converged to R 0.056 (R′ 0.066)(190 K data). The molecule has a trigonal-planar structure in which the maximum deviation from planarity is 0.03 Å.