Tuning coordination in s-block carbazol-9-yl complexes.

Chemistry : a European Journal
Fabrizio OrtuDeborah L Kays

Abstract

1,3,6,8-Tetra-tert-butylcarbazol-9-yl and 1,8-diaryl-3,6-di(tert-butyl)carbazol-9-yl ligands have been utilized in the synthesis of potassium and magnesium complexes. The potassium complexes (1,3,6,8-tBu4carb)K(THF)4 (1; carb = C12H4N), [(1,8-Xyl2-3,6-tBu2carb)K(THF)]2 (2; Xyl = 3,5-Me2C6H3) and (1,8-Mes2-3,6-tBu2carb)K(THF)2 (3; Mes = 2,4,6-Me3C6H2) were reacted with MgI2 to give the Hauser bases 1,3,6,8-tBu4carbMgI(THF)2 (4) and 1,8-Ar2-3,6-tBu2carbMgI(THF) (Ar = Xyl 5, Ar = Mes 6). Structural investigations of the potassium and magnesium derivatives highlight significant differences in the coordination motifs, which depend on the nature of the 1- and 8-substituents: 1,8-di(tert-butyl)-substituted ligands gave π-type compounds (1 and 4), in which the carbazolyl ligand acts as a multi-hapto donor, with the metal cations positioned below the coordination plane in a half-sandwich conformation, whereas the use of 1,8-diaryl substituted ligands gave σ-type complexes (2 and 6). Space-filling diagrams and percent buried volume calculations indicated that aryl-substituted carbazolyl ligands offer a steric cleft better suited to stabilization of low-coordinate magnesium complexes.

References

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Dec 15, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Deborah L Kays
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Feb 16, 2013·Inorganic Chemistry·Rhiannon S MoorhouseDeborah L Kays

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Citations

Jun 16, 2016·Angewandte Chemie·Aaron J BoutlandCameron Jones
Aug 22, 2015·Chemical Society Reviews·Deborah L Kays
Aug 15, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Conrad A P GoodwinDavid P Mills
Jun 28, 2018·Chemical Communications : Chem Comm·Jürgen PahlSjoerd Harder
Feb 5, 2019·Chemistry : a European Journal·Alexander Hinz
Jan 13, 2018·Chemical Communications : Chem Comm·Roberto Nolla-SaltielDeborah L Kays

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

CrysAlisPro
SHELXS
Samb V
OLEX2
SHELXL

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