Imaging Scientist; MetaCreations Corp.

Weiss, Benjamin E.

doi:10.5948/9781614441168.137

Cited by 1 publication

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“…[13,21] Another alkali-metal zincate, potassium tricyclopentadienylzincate, exists as a two-dimensional network. [22] Structures of solvent-free homoleptic alkylzincates are also few in number but include lithium tetramethylzincate, [23] which exists as a three-dimensional network, and MZn(CH 2 SiMe 3 ) 3 (M = Li, Na, K), which all exhibit supramolecular assemblies; a linear polymeric chain in the case of Li, and three-dimensional and two-dimensional coordination networks for Na and K, respectively. [11] Unsolvated mixed amido/alkyllithium zincates are also known.…”

Section: Synthesis Of a Solvent-free Heteroleptic Zincatementioning

confidence: 99%

Synthesis, Structure and Solution Studies on Mixed Aryl/Alkyl Lithium Zincates

et al. 2016

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Novel homo‐ and heteroleptic lithium zincates have been prepared by cocomplexation reactions of Zn(CH2SiMe3)2 and PhLi in low‐polarity hydrocarbon solvents. X‐ray crystallographic studies of products obtained by reacting the organometallic reagents in benzene or toluene yield the novel solvent‐free solid‐state arrangement [Li4Zn3Ph5(CH2SiMe3)5]⋡ (1). Combining Zn(CH2SiMe3)2 and PhLi in hexane in the presence of the polydentate N‐donors PMDETA (N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine) or TMEDA (N,N,N′,N′‐tetramethylethylenediamine) reveals monomeric heteroleptic [(PMDETA)LiZn(CH2SiMe3)2Ph] (2) and homoleptic [(TMEDA)LiZn(CH2SiMe3)3] (3), the result of a disproportionation process, respectively. NMR spectroscopic studies suggest that 2 and 3 retain their discrete contacted ion‐pair solid‐state structures in benzene solution. Variable‐temperature NMR spectroscopic studies of 2 in [D8]THF reveal a complex equilibrium also including [LiZn(CH2SiMe3)3], [LiZn(CH2SiMe3)Ph2] and [LiZnPh3], an equilibrium process analogous to that of 1 in THF. This study further highlights the complexity of these reactions, which at first would appear simple.

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