Multiple routes to the formation of a phosphine-bridged trirhodium dihydride cation, [Rh3{(.mu.-(Ph2PCH2))2PPh}2(H)2(.mu.-Cl)2(CO)2]+
Multiple routes to the formation of a phosphine-bridged trirhodium dihydride cation, [Rh3{(.mu.-(Ph2PCH2))2PPh}2(H)2(.mu.-Cl)2(CO)2]+
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形成膦桥二氢三铑阳离子 [Rh3{(μ-(Ph2PCH2))2PPh}2(H)2(μ-Cl)2(CO)2] 的多种途径
DOI：
10.1021/ic00242a022
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发表时间：
1986
影响因子：
4.6
通讯作者：
M. Olmstead
中科院分区：
文献类型：
--
作者：
A. Balch;J. Linehan;M. Olmstead
橙红色[Rh 3（# i-dpmp）2（H）2（^-Cl）2（CO）2][BPh4]（dpmp是双（（二苯基膦基）甲基）苯基膦）通过用氢处理[Rh 3（M-dpmp）2（CO）2（M-Cl）Cl][BPh 4]或[Rh 3（M-dpmp）2（M-CO）（CO）（M-Cl）Cl][BPh 4]的二氯甲烷溶液而形成，通过[Rh 3（Ai-dpmp）2（CO）3（u-Cl）Cl][BPh 4]与甲醛、多聚甲醛或乙醛水溶液的反应，或通过用二氢处理[Rh 3（M-dpmp）2（M-CO）2Cl 4][BPh 4]。深绿色[Rh 3（ju-dpmp）2（ju-CO）2C 14][BPh 4]通过用盐酸水溶液或氯化氢蒸气处理[Rh 3（ju-dpmp）2（CO）3（M-Cl）Cl][BPh 4]的二氯甲烷溶液形成。光谱数据表征这些配合物的报告。[Rh3 [（4 t-dpmp）2（H）2（CO）2（M-Cl）2][BPh_4·3CH_2Cl_2]的晶体结构属于P_2_n空间群（No.14），a= 14.498（2）k，B= 22.077（3）A，c= 28.353（3）A，λ = 99.86（1），Z= 4，在130 K时，对12079个反射，λ> 3（）和558个参数，R= 0.049，Rw= 0.054。该配合物由两个氯桥接的A-框架单元通过中心铑并排连接组成。在精炼过程中表现良好的Rh（2）主要位于中心铑上; Rh（2）-H距离为1.48（7）和1.55（7）A。结构和~ 1H NMR光谱证据表明，这些中间体和末端Rh（CO）Cl（P）2单元之间存在半桥相互作用。
Red-orange [Rh3 (# i-dpmp) 2 (H) 2^-Cl) 2 (CO) 2][BPh4](dpmp is bis ((diphenylphosphino) methyl) phenylphosphine) is formed by treatment of dichloromethane solutions of [Rh3 (M-dpmp) 2 (CO) 2 (M-Cl) Cl][BPh4] or [Rh3 (^-dpmp) 2 (^-CO)(CO)(M-Cl) Cl][BPh4] with dihydrogen, by the reaction of [Rh3 (Ai-dpmp) 2 (CO) 3 (u-Cl) Cl][BPh4] with aqueous formaldehyde, paraformaldehyde, or acetaldehyde, or by treatment of [Rh3 (M-dpmp) 2 (M-CO) 2Cl4][BPh4] with dihydrogen. Deep green [Rh3 (ju-dpmp) 2 (/u-C0) 2C14][BPh4] is formed by treatment of dichloromethane solutions of [Rh3 (^-dpmp) 2 (CO) 3 (M-Cl) Cl][BPh4] with aqueous hydrochloric acid or hydrogen chloride vapor. Spectroscopic data characterizing these complexes are reported.[Rh3 (^ t-dpmp) 2 (H) 2 (CO) 2 (M-Cl) 2][BPh4]'3CH2Cl2 crystallizes in the space group P2\/n (No. 14) with a= 14.498 (2) k, b= 22.077 (3) A, c= 28.353 (3) A, ß= 99.86 (1), and Z= 4 at 130 K, R= 0.049, Rw= 0.054 for 12079 reflectionswith/> 3 () and 558 parameters. The complex consists of two chloro-bridged A-frame units linked side-by-side through the central rhodium. The hydrides, which were well-behaved on refinement, are primarily localized on the central rhodium; Rh (2)-H distances are 1.48 (7) and 1.55 (7) A. Structural and* H NMR spectroscopic evidence suggests a semibridging interaction betweenthese hydrides and the terminal Rh (CO) Cl (P) 2 units.