Synthese, charakterisierung und reaktivität heterodinuklearer komplexe: [(CO)4(μ-PtBu2)Rh(CO)L](Fe-Rh) (L = CO2, HPtBu2), [(CO)3,Co(μ-H)(μ-PtBu2)Rh(CO)(HPtBu2)](Co-Rh)

Conformational Rigidity in Complexes [MCl(tBu2PH)3] (M = Rh, Ir)

“…In this light it is noteworthy that trans ‐[RhCl(CO)( t Bu 2 PH) 2 ] ( 3 ) seemed to show no tendency to the dissociation of CO during the DNMR studies, because no hints at the formation of the corresponding complex [{Rh(μ‐Cl)( t Bu 2 PH) 2 } 2 ] were indicated by NMR spectroscopy. Additionally, we investigated the thermolytic behavior of complex 3 by heating the compound in refluxing toluene for 3 h. These conditions were comparable to those of the preparation of [{Rh(μ‐Cl)( t Bu 2 PH) 2 } 2 ] by thermolysis of trans ‐[RhCl(C 2 H 4 )( t Bu 2 PH) 2 ] . Thus, after the described treatment, complex 3 was recovered unchanged and unambiguously indicated by its 31 P{ 1 H} NMR spectrum.…”

“…[9c] Operating in heptane at room temperature for several hours and applying a molar ratio Rh:P of 1:2 afforded the complex [{Rh(μ‐Cl)( t Bu 2 PH) 2 } 2 ] in nearly quantitative yield. The latter compound was described by us using another preparative route in two steps starting from [{Rh(μ‐Cl)(C 2 H 4 ) 2 } 2 ] . In the early stage of the reaction (during 1 h) of [{Rh(μ‐Cl)(coe) 2 } 2 ] with t Bu 2 PH in heptane, several phosphorus‐containing species were detected by 31 P{ 1 H} NMR spectroscopy.…”

Multimetallic Catalysis Based on Heterometallic Complexes and Clusters

“…The dinuclear complexes [(OC)LCo(μ-H){μ-P(t-Bu) 2 }Rh-(CO){HP(t-Bu) 2 }] (L = CO, HP(t-Bu) 2 ) were reported to homogeneously catalyze the hydroformylation of terminal olefins such as ethylene, propylene, and 1-octene with better selectivities for the linear isomers. 297 A cobalt−rhodium system, promoted by triphenylphosphine, enables a selective hydroformylation of dicyclopentadiene (DCPD) under relatively mild conditions. The main products obtained were those of paths A and B (Scheme 33), depending on the initial PPh 3 /metal ratio and the CO/H 2 pressure.…”

Synthesis and Molecular Structures of [Rh(η5‐C5H5)(coe)2] (coe =cis‐cyclooctene) and [Rh(η5‐C5H5)(cod)] (cod =cis,cis‐η4‐1,5‐cyclooctadiene)

“…For example, whereas the reaction of [{Rh(μ-Cl)(C 2 H 4 ) 2 (PtBu 2 H) 2 ], [5] the reaction of [{Rh(μ-Cl)(coe) 2 } 2 ] with the same phosphane leads to the complete loss of the alkene and the formation of the compound [{Rh(μ-Cl)(PtBu 2 H) 2 } 2 ]. [6] Herein, we report the synthesis and full characterization of the new compound [RhCp(coe) 2 ] (2) as well as of the complex [RhCp(cod)] (4) (cod = cis,cis-1.5-cyclooctadiene) with their molecular structures in the crystal being confirmed by X-ray crystallography.…”

“…In this context, cis ‐cyclooctene (coe) seemed to be a suitable candidate in this instance, since this alkene is known to be easily displaced from its Rh I complexes by other ligands. For example, whereas the reaction of [{Rh(μ‐Cl)(C 2 H 4 ) 2 } 2 ] with P t Bu 2 H results in the formation of trans ‐[RhCl(C 2 H 4 )(P t Bu 2 H) 2 ], the reaction of [{Rh(μ‐Cl)(coe) 2 } 2 ] with the same phosphane leads to the complete loss of the alkene and the formation of the compound [{Rh(μ‐Cl)(P t Bu 2 H) 2 } 2 ] . Herein, we report the synthesis and full characterization of the new compound [RhCp(coe) 2 ] ( 2 ) as well as of the complex [RhCp(cod)] ( 4 ) (cod = cis , cis ‐1.5‐cyclooctadiene) with their molecular structures in the crystal being confirmed by X‐ray crystallography.…”