Preparation and Control of Coordinatively Unsaturated Active Species

用Dppe、Dppp、Dppb、DIOP、Dppf、BINAP等膦配位合成了五种配位的Ru配合物[RuH(P-P)2]Pf6，其中Dppe为1，2-二(二苯基膦)乙烷，DPP为1，3-二(二苯基膦)丙烷，Dppb为1，4-二(二苯基膦)丙烷，2，3-o-isopropylidene-2，3-dihydroxy-1，4-bis(diphenylphosphino)butane，为1，2-双(二苯基膦)二茂铁，BINAP为2，2‘-双(二苯基膦)-1，1’-联萘。这些配合物的核磁共振研究表明，它们在溶液中含有第6个配体，如溶剂、氮分子等。当配合物与膦形成大的螯合环时，观察到与膦的苯基相互作用的顺式异构体占主导地位。在Ar、N和H气氛下对DPPB的进一步研究表明，这种无规相互作用强于氮分子或溶剂的配位，而弱于分子氢的配位。民进党…的结构X-射线衍射仪测定到更多的f-络合物，表明dppf的空间位阻导致了顺式结构。氢分子与该络合物配位，得到新型的分子氢络合物。H_2配体的T_1值表明H_2与原始氢化物配体是等价的，换言之，这是一个三氢化物络合物。由二烷基形成的活性物种是茂锆烯(II)-烯烃配合物。用X-射线衍射法确定了化合物的结构。二茂锆烯类化合物与另一种烯烃反应，得到了具有99%区域选择性和99%立体选择性的烯烃-烯烃交叉偶联产物。此外，对其机理的详细研究还导致了新的骨架重排的发展：在锆石或半环戊烷衍生物的情况下，通过碳-碳键的激活来进行新的骨架重排。这种新方法可以选择性地将α-位的甲基转移到β-位。较少

Five coordinate ruthenium complexes [RuH(P-P)_2]PF_6 were prepared with various phosphines such as dppe, dppp, dpppb,diop, dppf, binap, where dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, dppb is 1,4-bis(diphenylphosphino)-propane, diop is 2,3-o-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, dppf is 1,2-bis(diphenylphosphino)ferrocene, binap is 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl. The NMR studies of these complexes indicated that they have a 6th ligand such as solvent, nitrogen molecule and so on, in solution. When complexes have large chelate rings with phosphines, observed were predominant formation of cis isomers with agostic interactions with phenyl group of phosphines. Further investigations with dppb under argon, nitrogen or hydrogen atmosphere revealed that this agostic interaction was stronger than the coordination of nitrogen molecule or solvent, and weaker than molecular hydrogen coordination. The structure of dpp … More f-complex was determined by x-ray study, indicating the cis-structure due to the steric hindrance of dppf. Hydrogen molecule coordinated to this complex to give novel type of molecular hydrogen complex. T_1 value of H_2 ligand of this complex showed that the H_2 and original hydride ligands are equivalent, in other word, this was a trihydride complex.In the case of zirconium species, we found the followings. The active species quantitatively formed from zirconocenedialkyls were zirconocene(II) olefin complexes. The structure of zirconocenestilbene complex was determined by x-ray analysis. Reactions of zirconocene olefin complexes with another olefins gave olefin-olefin cross coupling products with >99% of regio-selectivities and >99% of stereo-selectivities. In addition the detail investigations of its mechanism led the development: of novel skeleton rearrangement by carbon-carbon bond activation in the case of zircona- or hafnacyclopentane derivatives. Methyl group of alpha-position could be transferred to beta-position selectively by this novel method. Less