Synthesis and structures of monomeric divalent germanium and tin compoundscontaining a bulky diketiminato ligand

Citation
Yq. Ding et al., Synthesis and structures of monomeric divalent germanium and tin compoundscontaining a bulky diketiminato ligand, ORGANOMETAL, 20(6), 2001, pp. 1190-1194
Citations number
38
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
02767333 → ACNP
Volume
20
Issue
6
Year of publication
2001
Pages
1190 - 1194
Database
ISI
SICI code
0276-7333(20010319)20:6<1190:SASOMD>2.0.ZU;2-A
Abstract
eaction of the beta -diketiminato lithium salt Li(OEt2) [HC(CMeNAr)(2)] (AT = 2,6-i-Pr2C6H3) with GeCl2. (dioxane) and SnCl2 in diethyl ether provided the monomeric complexes [HC-(CMeNAr)(2)]MCl (M = Ge (2), Sn (3), respectiv ely) with a three-coordinated metal center. The reductive dehalogenation re actions of 3 with C8K and LiAlH4 afforded [HC(CMeNAr)(2)](2)Sn (7) and [HC( CMeNAr)(2)]AlH2, respectively. The metathesis reactions of 3 with t-BuLi, A gSO3CF3, and NaN3 resulted in the formation of [HC(CMeNAr)(2)]Sn(t-Bu) (4), [HC(CMeNAr)(2)]-Sn(OSO2CF3) (5), and [HC(CMeNAr)(2)]SnN3 (6), respectively . Compounds 2, 3, 5, and 7 were characterized by single-crystal X-ray struc tural analysis. The structures indicate that the beta -diketiminato backbon e is essentially planar and the metal centers reside in distortedtetrahedra l environments with one vertex occupied by a lone pair of electrons. The bo nd angles at the metal center are in the range 85.2(8)-106.8(2)degrees, and the most acute angle is associated with the bite of the chelating ligand.