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）制备了BIS [二氢化曲（3,5-双（三氟甲基）吡唑基）硼酸盐]钴酸盐[制备了钴]，并通过X射线晶体学分析确定结构。钴中心以平方规划仪的方式与四个吡唑基团协调，并在轴向位置的两个B-H基团完全构成完全扭曲的八面体构型。这与已知的非降解和3个，5-二甲基取代的吡唑理硼酸衍生物形成鲜明对比，这些衍生物看起来像Inn in Ins a Inn具有四面体构型相似的相似的镍配合物，具有B-H-M-M Agostic相互作用。制备CF_3），并通过X射线晶体学确定含有B-H-Ru arpostic相互作用的结构。基于与CO的反应性，估计Agostic相互作用的强度在顺序下降低，ME> H * CF_3。（3）BIS（Triphenylylasphophine）[Dihydrobis（3，5-R_2-R_2-吡唑基）Botare] Rhodium复合物（R = H，ME，CF_3）由X Ray Cyrycroprication确定。菱形中心以方形计划者方式与四个吡唑基团进行协调。在这些复合物中未观察到B-H-RH的相互作用。（4）ETA^3-酰基和idenenyl [Hydyotris（3,5-R_2-吡唑基）硼酸盐]钯配合物（R = H，ME，CF_3），制备了结构，并通过X射线晶体学分析确定结构。通过NMR光谱研究研究了它们在溶液中的转速行为。