Di‐(μ‐amido)dirhodium Complexes: Structure of [Rh₂(μ‐(NH)₂naphth)I₂(CO)₂(PPh₃)₂]

Abstract

tightly bonded to uranium. In contrast to metal-carbon single bonds, where CC single bonds form during insertion reactions, insertion at the U=C double bond leads to a new unsaturated ligand.The reaction of 3 and C6HIINC (molar ratio 1 : 1, 1 h) in ether produces a red solution from which 4 can be isolated as red crystals in 53% yield after evaporation of the solvent followed by recrystallization from a 1 : 1 benzene-pentane mixture. The 'H-NMR spectrum shows paramagnetically shifted peaks [7], and the IR spectrum is complex, but does not exhibit a peak at ca. 2136 cm-', a characteristic frequency for C6HIINC ["I. 4 can be stored for months in vacuo or under anhydrous nitrogen, but decomposes within seconds if exposed to the atmosphere. It is very soluble in aromatic solvents and ethers, but only slightly soluble in aliphatic hydrocarbons.

Transition Metal Complexes with the Proton Sponge 4,9-Dichloroquino[7,8-h]quinoline: Highly Twisted Aromatic Systems and an Extreme “Out-of-Plane” Position of the Coordinated Transition Metal Atom

“…[6] Although 1,8-diaminonaphthalene [7,8] is not a proton sponge a few transition metal complexes are known.…”

“…In addition, this compound is planar and not helical and thus very suitable as a ligand for metal complexes. 1 is in comparison a better ligand than the widely used o-phenanthroline for two reasons: The unusually high basicity of 1 (pK a 10.9 [8] ) compared to o-phenanthroline (pK a 4.81 [9] ) and the short nitrogen ± nitrogen distance of 2.685 forces the complexed metal atom into an ªout-of-planeº position. This confers a very high thermal stability on the metal complexes.…”

“…The 4-bromothiazole 7 was converted into a carbon nucleophile by a halogen ± metal exchange reaction. [8] After transmetalation with zinc chloride the aryl metal compound reacted regioselectively with 6 to afford the desired intermediate 3 (Scheme 2).…”

Steric Effects in the Oxidative Addition of MeI to a Sulfido-Bridged ZrRh2Early–Late Heterobimetallic Compound

“…The spectroscopic data for 6 are very similar to those described for 5 and consequently should be isostructural (Scheme 3). In particular, the 31 The intermetallic distance found in complex 5, very similar to the found in the starting material 2, is not indicative of the presence a metal-metal bond between both coordinatively unsaturated rhodium centers. However, the spectroscopic data in complexes 5 and 6 suggest the presence of a dative bonding interaction Rh(I)→Rh(III) between the metal centers.…”

Quest for metal/NH bifunctional bioinspired catalysis in a dinuclear platform

“…1,2,5, 7 Oro and co-workers synthesized the diamidobridged Rh II 2 complex 11 through dinuclear oxidative addition of I 2 to the Rh I 2 amido complex [{Rh(CO)(PPh 3 )} 2 {m-(NH) 2 C 10 H 6 }] as early as 1984. 24 Later, they reported di-and trimerization reactions of terminal alkynes catalyzed by the related diiridium complex 12 as shown in Scheme 7. 25 The amido proton, however, seems inert towards deprotonation and irresponsible for these intriguing reactions and catalysis; the amido ligand appears just to fix the two metal centers in close proximity.…”