Creation of Substitution Labile Pyrazolylborate Metal Complexes

取代不稳定的吡唑基硼酸盐金属配合物的制备

基本信息

批准号：
09640675
负责人：
YAMAZAKI Hiroshi
金额：
$ 0.96万
依托单位：
CHUO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

(1) Bis[dihydrobis(3,5-bis(trifluoromethyl)pyrazolyl)borate]cobalt was prepared and the structure was determined by X ray crystallographic analysis. The cobalt center is coordinated to four pyrazolyl groups in a square planner manner and to two B-H groups at the axial positions forming totally a distorted octahedral configuration. This is in marked contrast to those of known non-substituted and 3, 5-dimethyl substituted pyrazolylborate derivatives which appear inn a tetrahedral configuration Similar nickel complex having a B-H-M agostic interaction was prepared.(2) Bis(triphenylphosphine)[dihydrobis(3,5-R_2-pyrazolyl)borate]ruthenium hydrides (R=H, Me, CF_3) were prepared and the structures containing a B-H-Ru agostic interaction were determined by X ray crystallography. Based on the reactivity with CO, strength of the agostic interaction was estimated to decrease in the order, Me> H * CF_3.(3) Bis(triphenylphosphine)[dihydrobis(3, 5-R_2-pyrazolyl)borate]rhodium complexes (R=H, Me, CF_3) were prepared and the structures were determined by X ray crystallographic analysis. The rhodium centers are coordinated in a square planner manner to the four pyrazolyl groups. No B-H-Rh agostic interactions were observed in these complexes.(4) eta^3-Allyl and indenyl[hydrotris(3,5-R_2-pyrazolyl)borate]palladium complexes (R=H, Me, CF_3) were prepared and the structures were determined by X ray crystallographic analysis. Their fluxional behavior in solution were studied by NMR spectroscopy.

(1)制备双[二氢双(3,5-双(三氟甲基)吡唑基)硼酸]钴并通过X射线晶体分析确定结构。钴中心以正方形平面方式与四个吡唑基配位，并在轴向位置与两个B-H基团配位，形成完全扭曲的八面体构型。这与以四面体构型出现的已知的未取代的和3，5-二甲基取代的吡唑基硼酸酯衍生物形成鲜明对比。制备了具有B-H-M激动相互作用的类似镍络合物。 (2)双(三苯基膦)[二氢双(3，制备了氢化5-R_2-吡唑基)硼酸酯]钌氢化物(R=H,Me,CF_3)，其结构包含B-H-Ru 激动相互作用通过 X 射线晶体学测定。根据与 CO 的反应性，预计相互作用的强度按 Me> H * CF_3 的顺序降低。(3) 双(三苯基膦)[二氢双(3, 5-R_2-吡唑基)硼酸盐]铑配合物 (R制备了=H、Me、CF_3)并通过X射线晶体分析确定了结构。铑中心以方形平面方式与四个吡唑基配位。在这些配合物中没有观察到B-H-Rh的相互作用。(4)制备了eta^3-烯丙基和茚基[氢三(3,5-R_2-吡唑基)硼酸酯]钯配合物(R=H,Me,CF_3)并通过X射线晶体学分析确定结构。通过核磁共振波谱研究了它们在溶液中的流动行为。