Novel highly electron-deficient quinoxaline-annulated 1,3,2-diazagermol- and diazastannol-2-ylidenes, stabilized as LiCl adducts

作者：Ullah Farman; Kuhl Olaf; Rehman Wajid; Jones Peter G; Heinicke Joachim^*

来源：Polyhedron, 2010, 29(3): 1041-1048.

DOI：10.1016/j.poly.2009.12.014

• Germylene
• Stannylene
• Germanium heterocyctes
• Annulation effect
• Diaminoquinoxaline

Reaction of 2,3-bis(neopentylamino)quinoxaline (1) with nBuL1 and GeCl(4) or GeCl(2) (dioxane) (molar ratio 1.2.1) in THF furnished highly moisture-sensitive Ge(IV) and Ge(II) heterocycles 2a and 3a, respectively The quinoxaline-annulated N-heterocyclic germylene (quinNHGe) 3a is stable only in the presence of U(THF), and exhibits electrophilic properties associated with the strongly electron-withdrawing annulation. Coordination of chloride at Ge(II) and of Li* at nitrogen is assumed, as found in crystals of a bis(quinoxaline)-annulated eight-membered NHGe LiCl adduct. Addition of dineopentyl-benzimidazol-2-ylidene (bnNHC) provides a labile bnNHC-qumNHGe adduct 4 as indicated by strong downfield coordination shift of the NMR signal for the carbene donor atom. Attempts to grow single crystals led to decomposition and protonation of the carbene forming the bis(benzimidazolium) salt 5 with Li(2)(THF)(2)Cl(4)(2-) anion Introduction of 2-methoxyethyl or 2-dimethylaminoethyl side arms as chelating functional groups into the diaminoquinoxalines 6 and 7 and Subsequent reaction with 2 nBuLi/GeCl(2) (dioxane) did not markedly stabilize the resulting donor-substituted quinNHGe 8 and 9 Related silicon (2b) and tin heterocycles (3c) were synthesised for comparison The quinoxaline-annulated N-heterocyclic stannylene 3c exhibits all extreme (119)Sn upfield shift compared to other N-heterocyclic stannylenes, suggesting higher coordination at tin.

• 出版日期2010-2-19