Synthesis, Structure, and Reactivity of Rhodium Bipyridine Compounds: Formation of a Rh^II Hydrido Cluster and a Rh^III Peroxido Complex

Abstract

Treatment of [Rh(µ-Cl)(coe) 2 ] 2 (coe = cyclooctene) with 4,4Ј-di-tert-butyl-2,2Ј-bipyridine (tbbpy) gives the bipyridine complex [Rh(Cl)(tbbpy)(coe)] (1). A subsequent reaction with dihydrogen results in the formation of the cluster [{Rh(Cl)(H)-(tbbpy)}] 4 (2). The reaction of [Rh(µ-Cl)(coe) 2 ] 2 with tbbpy in thf followed by the addition of CNtBu affords [Rh(Cl)(tbbpy)-

Synthesis and Structures of Fluorinated (β‐Diketiminato)rhodium Complexes: Si–H Activation of Silanes at a Carbonyl Complex

“…[24d,24e] The presence of three absorption bands in the IR spectra of diisonitrile complexes has been documented in the literature. [24] The 13 C{ 1 H} NMR spectrum exhibits an unusually high-field-shifted [22] doublet resonance for the rhodium-bound carbon atoms at δ = 147.8 ppm with a rhodium-carbon coupling constant of 1 J Rh,C = 65.1 Hz. The structure of 4 in the solid state was determined by X-ray crystallography ( Figure 3); selected bond lengths and angles are summarized in Table 4.…”

“…The solid-state IR spectrum of 4 shows three absorption bands at ν = 2137, 2094, and 2064 cm -1 for two CNtBu ligands at a rhodium(I) complex. [22][23][24] Spectra measured in toluene and THF also reveal three bands at ν = 2137, 2095, and 2061 cm -1 (toluene) and at ν = 2139, 2096, and 2061 cm -1 (THF). However, DFT calculations to model the IR spectrum of 4 in the gas phase show only two absorption bands at ν = 2189 and 2133 cm -1 (B3LYP/cc-pvdz).…”

“…The formal oxidation state of metal centers in transitionmetal complexes that contain π-accepting ligands such as carbonyl [7,12a,20,21] or isocyanido ligands [22][23][24] can be esti-mated by characteristic absorption bands of these π-acceptor ligands in the IR or Raman spectra. The use of such ligands might therefore provide a helpful tool to obtain information on the electronic properties of the metal center.…”

“…(4) tion bands at ν = 2140, 2103, and 2068 cm -1 for two CNtBu ligands in the IR spectrum (ATR). [22][23][24] The 13 C{ 1 H}-NMR spectrum features a doublet resonance signal at δ = 150.5 ppm with a rhodium-carbon coupling constant of 1 J Rh,C = 63.0 Hz. The structure of 5 in the solid state was also determined by X-ray crystallography ( Figure 4); selected bond lengths and angles are summarized in Table 5.…”

“…These values are comparable to the data in other isocyanide complexes. [22][23][24] The rhodium isocyanide units exhibit angles of Rh1-C18-N3 177.5(2)°and Rh1-C23-N4 176.6(2)°. (4) tion bands at ν = 2140, 2103, and 2068 cm -1 for two CNtBu ligands in the IR spectrum (ATR).…”