K[Al4(PPh2)7PPh]: An AlII Phosphanide / Phosphinidene Intermediate on the Path to AlP Formation

Mayo, Dennis H.; Peng, Yang; DeCarlo, Samantha; Li, Xiang; Lightstone, James M.; Zavalij, Peter Y.; Bowen, Kit H.; Schnöckel, Hansgeorg; Eichhorn, Bryan W.

doi:10.1002/zaac.201300359

Cited by 6 publications

(2 citation statements)

References 21 publications

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“…Each aluminum is four‐coordinate, bound to two other aluminum atoms and two PPh 2 ligands in a distorted tetrahedral geometry. The average Al−P bond distance in 1 is 2.370 Å (Al−P range=2.368–2.379 Å) and is within the range of previously reported aluminum phosphide complexes [14–15] . Average P−Al−Al angles are 109.8±1.3° and are close to the expected tetrahedral angle of 109.5°.…”

Section: Resultssupporting

confidence: 83%

“…The average AlÀ P bond distance in 1 is 2.370 Å (AlÀ P range = 2.368-2.379 Å) and is within the range of previously reported aluminum phosphide complexes. [14][15] Average PÀ AlÀ Al angles are 109.8 � 1.3°and are close to the expected tetrahedral angle of 109.5°. The average PÀ AlÀ P angle is 134.0 � 0.5°and is significantly wider than the expected tetrahedral angle to better facilitate lone pair donation from phosphorus to lithium.…”

Section: Solid-state Structuressupporting

confidence: 63%

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Unique Aluminum Clusters Stabilized by Cation‐Ligand Cooperativity

Davis,

Stevens,

DeCarlo

et al. 2024

Eur J Inorg Chem

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Two novel cyclic Al3 clusters, [Li2Al3(PR2)6]•2(Et2O) [R = Ph (1), Cy (2)] were synthesized through salt metathesis of metastable AlCl·(Et2O)n solutions with LiPR2. Both complexes were characterized by single crystal X‐Ray diffraction and their solid state and electronic structures are compared to previously reported cyclic Al3 clusters. Compounds 1 and 2 were further characterized using density functional theory (DFT) methods to understand the nature of the free electron and the three center two electron Al‐Al bonds. Calculations revealed that both clusters are influenced by pseudo‐Jahn Teller distortion and are likely in equilibrium between two low energy bonding states. The solid‐state structures of 1 and 2 are unique among Al3 clusters while the electronic structure is isoelectronic to the previously reported [Sit4Al3] making 1 and 2 rare examples in aluminum chemistry of clusters containing isoelectronic cores and different ligand spheres. The effects of the phosphide ligand sphere and strongly coordinated lithium atoms are discussed in detail.

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Section: Resultssupporting

confidence: 83%

Section: Solid-state Structuressupporting

confidence: 63%