Ferrocenylaluminum-pyridine adducts, lithium tetra(ferrocenyl)alanate, and the molecular structure of tri(ferrocenyl)aluminum-pyridine

Wrackmeyer, Bernd; Klimkina, Elena V.; Ackermann, Tamara; Milius, Wolfgang

doi:10.1016/j.ica.2009.05.019

Cited by 3 publications

(2 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As expected, their structures are very similar to the known [1.1]FCPs ( 1a , 1b ; Chart ). Ferrocenyl-substituted aluminum and gallium compounds are rare . The new bis(ferrocenyl) compounds of aluminum ( 5a , 6a ) and gallium ( 5b , 6b ) equipped with two different ligands capable of intramolecular donation were prepared.…”

Section: Discussionmentioning

confidence: 99%

[1.1]Ferrocenophanes and Bis(ferrocenyl) Species with Aluminum and Gallium as Bridging Elements: Synthesis, Characterization, and Electrochemical Studies

Bagh¹,

Breit²,

Harms

et al. 2012

Inorg. Chem.

View full text Add to dashboard Cite

Salt-metathesis reactions between dilithioferrocene (Li(2)fc·2/3tmeda) and intramolecularly coordinated aluminum and gallium species RECl(2) [R = 5-Me(3)Si-2-(Me(2)NCH(2))C(6)H(3); E = Al (2a), Ga (2b); and R = (2-C(5)H(4)N)Me(2)SiCH(2); E = Al (3a), Ga (3b)] gave respective [1.1]ferrocenophanes ([1.1]FCPs). Those obtained from 2a and 2b, respectively, were isolated as analytically pure compounds and fully characterized including single-crystal X-ray structure determinations [4a (Al): 43%; 4b (Ga): 47%]. Bis(ferrocenyl) compounds of the type REFc(2) [R = 5-Me(3)Si-2-(Me(2)NCH(2))C(6)H(3); E = Al (5a), Ga (5b); and R = (2-C(5)H(4)N)Me(2)SiCH(2); E = Al (6a), Ga (6b)] and R(2)SiFc(2) [R = Me (7(Me)); Et (7(Et))] were prepared, starting from respective element dichlorides and lithioferrocene (LiFc). Molecular structures of 6a, 7(Me), and 7(Et) were solved by single-crystal X-ray analyses. One of the two Fc moieties of 6a was bent toward the open coordination site of the aluminum atom. The measured dip angles α* of the two independent molecules in the asymmetric unit were 11.9(5) and 13.3(5)°, respectively. The redox behavior of [1.1]FCPs 4 and bis(ferrocenyl) species 5, 6, 7, and (Mamx)EFc(2) [Mamx = 2,4-tBu(2)-6-(Me(2)NCH(2))C(6)H(2); E = Al (8a), Ga (8b)] were investigated with cyclic voltammetry. While all gallium and silicon compounds gave meaningful and interpretable data, all aluminum compounds were problematic with the exception of 8a. Aluminum species, compared to respective gallium species, are more sensitive and, presumably, fluoride ions or residual water from the electrolyte and solvent are causing degradation. The splitting between the formal potentials for bis(ferrocenyl) species was significantly smaller (5b, 6b, and 8b: ΔE°' = 0.138-0.159 V) than that of the [1.1]FCP 4b (ΔE°' = 0.309 V). These results were explained by assuming an electrostatic interaction between the two iron centers; differences between bis(ferrocenyl) species and [1.1]FCPs are likely due to a more effective solvation of Fe-containing moieties in the more flexible bis(ferrocenyl) species.

show abstract

Section: Discussionmentioning

confidence: 99%

[1.1]Ferrocenophanes and Bis(ferrocenyl) Species with Aluminum and Gallium as Bridging Elements: Synthesis, Characterization, and Electrochemical Studies

Bagh¹,

Breit²,

Harms

et al. 2012

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…Organoaluminum compounds are well known to form 1:1 adducts with a wide range of neutral donor ligands owing to their Lewis acidity . Such Lewis acid–base complexes are kinetically stable, even if the neutral ligand contains acidic protons, a nitrile, imine, or carbonyl functionality, or an activated (hetero)aromatic ring. , The insertion of pyridine derivatives into the metal–carbon bond of organometallic compounds to give metalated 1,2- or 1,4-dihydropyridines (DHPs) is of interest in organic chemistry, since 1,4-DHPs are well-known calcium antagonists and 1,2-DHPs have been shown to also inhibit the calcium channel . Whereas organometallic compounds of groups 1 and 2, many transition metals, lanthanides, and actinides react with pyridine under insertion, metalation, or ring cleavage, the reactivity of group 13 organometallics is largely dominated by adduct formation (Scheme : a–d). ,− …”

Section: Introductionmentioning

confidence: 99%

Reactivity of Tris(allyl)aluminum toward Pyridine: Coordination versus Carbometalation

2011

View full text Add to dashboard Cite

Tris(allyl)aluminum as its THF adduct, [Al(η 1 -C 3 H 5 ) 3 (THF)] (1), reacted with pyridine either under substitution to give [Al(η 1 -C 3 H 5 ) 3 (py)] (7) (py = pyridine) or under carbometalation to give N-metalated 2-allyldihydropyridine depending on the solvent. The substituent pattern of the pyridine substrate and the aluminum center's electrophilicity in [Al(η 1 -C 3 H 5 ) 3 (L)] (L = neutral ligand) influenced the outcome of the reaction. Reactions of one N-metalated dihydropyridine with electrophiles have been studied. A crystalline derivative of tris(allyl)aluminum, [Al(η 1 -C 3 H 5 ) 3 (OPPh 3 )] (2), and tetrakis(allyl)aluminate in the ion pair [K(15-crown-5) 2 ][Al(η 1 -C 3 H 5 ) 4 ] (4) were characterized by single-crystal X-ray diffraction and shown to contain four-coordinate aluminum centers.

show abstract

Homoleptic Ferrocenyl Stibine and Bismuthine: Synthesis and Characterization

Rocio Rosales,

Villamizar C.,

Dymarcus

et al. 2023

Russ. J. Inorg. Chem.

View full text Add to dashboard Cite

Ferrocenylaluminum-pyridine adducts, lithium tetra(ferrocenyl)alanate, and the molecular structure of tri(ferrocenyl)aluminum-pyridine

Cited by 3 publications

References 24 publications

[1.1]Ferrocenophanes and Bis(ferrocenyl) Species with Aluminum and Gallium as Bridging Elements: Synthesis, Characterization, and Electrochemical Studies

[1.1]Ferrocenophanes and Bis(ferrocenyl) Species with Aluminum and Gallium as Bridging Elements: Synthesis, Characterization, and Electrochemical Studies

Reactivity of Tris(allyl)aluminum toward Pyridine: Coordination versus Carbometalation

Homoleptic Ferrocenyl Stibine and Bismuthine: Synthesis and Characterization

Contact Info

Product

Resources

About