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Monomeric Cp^3tAl(i): synthesis, reactivity, and the concept of valence isomerism.

ABSTRACT: With the isolation of Cp^3tAl (1), the first monomeric Cp-based Al(i) species could be realized in a pure form via a three-step reaction sequence (salt elimination/adduct formation/adduct cleavage) starting from readily available AlBr₃. Due to its monomeric structure, reactions involving 1 were found to proceed more selectively, faster, and under milder conditions than for tetrameric (Cp*Al)₄. Thus, 1 readily formed simple Lewis acid-base adducts with tBuAlCl₂ (6) and AlBr₃ (7), reactions that before have always been interfered with by the presence of aluminum halide bonds. In addition, the 2?:?1 reaction of 1 with AlBr₃ enabled the realization of the very rare trialuminum adduct species 8. 1 also reacted rapidly with N₂O and PhN₃ at room temperature to afford Al₃O₃ and Al₂N₂ heterocycles 9 and 10, respectively. With the structural characterization of products 4 and 5, the reaction of monovalent 1 with Cp^3tAlBr₂ (2) provided the first experimental evidence for the concept of valence isomerism between dialanes and their Al(i)/Al(iii) Lewis adducts.

SUBMITTER: Hofmann A

PROVIDER: S-EPMC6429597 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Monomeric Cp3tAl(i): synthesis, reactivity, and the concept of valence isomerism.

Hofmann Alexander A Tröster Tobias T Kupfer Thomas T Braunschweig Holger H

Chemical science 20190114 11

With the isolation of Cp3tAl (1), the first monomeric Cp-based Al(i) species could be realized in a pure form via a three-step reaction sequence (salt elimination/adduct formation/adduct cleavage) starting from readily available AlBr3. Due to its monomeric structure, reactions involving 1 were found to proceed more selectively, faster, and under milder conditions than for tetrameric (Cp*Al)4. Thus, 1 readily formed simple Lewis acid-ba ...[more]

PMID: 30996931

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Project description:Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.

Project description:Two new monomeric Cu(II) alkoxide complexes were prepared and fully characterized as models for intermediates in copper/radical mediated alcohol oxidation catalysis: Tp(tBuR)Cu(II)OCH2CF3 with Tp(tBu) = hydro-tris(3-tert-butyl-pyrazol-1-yl)borate 1 or Tp(tBuMe) = hydro-tris(3-tert-butyl-5-methyl-pyrazol-1-yl)borate 2. These complexes were made as models for potential intermediates in enzymatic and synthetic catalytic cycles for alcohol oxidation. However, the alkoxide ligands are not readily oxidized by loss of H; instead, these complexes were found to be hydrogen atom acceptors. They oxidize the hydroxylamine TEMPOH, 2,4,6-tri-t-butylphenol, and 1,4-cyclohexadiene to the nitroxyl radical, phenoxyl radical, and benzene, with formation of HOCH2CF3 (TFE) and the Cu(I) complexes Tp(tBuR)Cu(I)-MeCN in dichloromethane/1% MeCN or 1/2 [Tp(tBuR)Cu(I)]2 in toluene. On the basis of thermodynamics and kinetics arguments, these reactions likely proceed through concerted proton-electron transfer mechanisms. Thermochemical analyses give lower limits for the "effective bond dissociation free energies (BDFE)" of the O-H bonds in 1/2[Tp(tBuR)Cu(I)]2 + TFE and upper limits for the free energies associated with alkoxide oxidations via hydrogen atom transfer (effective alkoxide ?-C-H BDFEs). These values are summations of the free energies of multiple chemical steps, which include the energetically favorable formation of 1/2[Tp(tBuR)Cu(I)]2. The effective alkoxide ?-C-H bonds are very weak, BDFE ? 38 ± 4 kcal mol(-1) for 1 and ?44 ± 5 kcal mol(-1) for 2 (gas-phase estimates), because C-H homolysis is thermodynamically coupled to one electron transfer to Cu(II) as well as the favorable formation of the 1/2[Tp(tBuR)Cu(I)]2 dimer. Treating 1 with the H atom acceptor (t)Bu3ArO(•) did not result in the expected alkoxide oxidation to an aldehyde, but rather net 2,2,2-trifluoroethoxyl radical transfer occurred to generate an unusual 2-substituted dienone-ether product. Treating 2 with (t)Bu3ArO(•) gives no reaction, despite evidence that overall ligand oxidation and formation of 1/2[Tp(tBuMe)Cu(I)]2 is significantly exoergic. The origin of this lack of reactivity may be due to insufficient weakening of the alcohol ?-C-H bond upon complexation to copper.

Dataset Information

Monomeric Cp^3tAl(i): synthesis, reactivity, and the concept of valence isomerism.

Publications

Monomeric Cp<sup>3t</sup>Al(i): synthesis, reactivity, and the concept of valence isomerism.

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