Substitution and hydrogenation reactions on rhodium(I)-ethylene complexes of the hydrotris(pyrazolyl)borate ligands Tp′ (Tp′ = Tp, TpMe2)

被引：44

作者：

Nicasio, MC

Paneque, M

Pérez, PJ

Pizzano, A

Poveda, ML

Rey, L

Sirol, S

Taboada, S

Trujillo, M

Monge, A

Ruiz, C

Carmona, E

机构：

[1] Univ Seville, CSIC, Inst Invest Quim, Dept Quim Inorgan, Seville 41092, Spain

[2] CSIC, Inst Ciencia Mat Madrid, E-28049 Madrid, Spain

来源：

INORGANIC CHEMISTRY | 2000年 / 39卷 / 02期

关键词：

D O I：

10.1021/ic990419u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The bis(ethylene) Rh species Tp(Me2)Rh(C2H4)(2) (1*) (Tp(Me2) = tris(3,5-dimethyl-1-pyrazol-1-yl)hydroborate) has been obtained from [RhCl(C2H4)(2)](2) and KTp(Me2). Complex 1* easily decomposes in solution to give mainly the butadiene species Tp(Me2)-Rh(eta(4)-C4H6). In the solid state its thermal decomposition follows a different course and the allyl Tp(Me2)RhH(syn-C3H4Me) is cleanly obtained as a mixture of exo and endo isomers. The complexes Tp'Rh(C2H4)(2) (Tp' = Tp, Tp(Me2)) afford the monosubstituted species Tp'Rh(C2H4)(PR3) upon reaction with PR3 but react differently with L = CO or CNR: the Tp compound gives dinuclear [TpRh](2)(mu-L)(3) complexes, while, in the case of 1*, Tp(Me2)Rh(C2H4)(L) species are obtained. The ethylene ligand of complexes Tp(Me2)Rh(C2H4)(PR3) is labile, and several peroxo compounds of composition Tp(Me2)Rh(O-2)(PR3) have been isolated by their reaction with O-2 All the mononuclear Rh(I) complexes are formulated as 18e(-) trigonal bipyramidal species on the basis of IR and NMR spectroscopic studies. A. series of dihydride complexes of Rh(III) of formulation Tp'RhH2(PR3) have been prepared by the hydrogenation of the corresponding ethylene derivatives. Complexes [TpRh](2)(mu-CNCy)(3), Tp(Me2)Rh(C2H4)(PEt3), and Tp(Me2)-Rh(O-2)(PEt3) have been further characterized by X-ray diffraction studies.

引用

页码：180 / 188

页数：9

共 59 条

[1] THE ADDITION OF ISONITRILES TO [(MO(CO)2(ETA-C5H5))2], [(W(CO)2(ETA-C5H5))2] - SYNTHESES AND PROPERTIES OF [M2(MU-ETA-2-CNR)(CO)4(ETA-C5H5)2] (M = MO OR W, R = ME OR BUT) AND [(MO(CNME)(CO)2(ETA-C5H5))2], [(MO(CNBUT)(CO)2(ETA-C5H5))2] - X-RAY CRYSTAL-STRUCTURES OF [MO2(MU-ETA-2-CNBUT)(CO)4(ETA-C5H5)2] AND [(MO(CNBUT)(CO)2(ETA-C5H5))2] [J].