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Synthesis and Structural Diversity of ZnCl 2 and Zn(C 6 F 5 ) 2 Complexes of a Phosphinimine Ligand
Author(s) -
Wheaton Craig A.,
Ireland Benjamin J.,
Hayes Paul G.
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100355
Subject(s) - chemistry , dibenzofuran , steric effects , diethylzinc , ligand (biochemistry) , denticity , zinc , aryl , stereochemistry , crystallography , medicinal chemistry , crystal structure , organic chemistry , catalysis , receptor , biochemistry , alkyl , enantioselective synthesis
Zinc complexes of the potentially bidentate neutral monophosphinimine ligand 4‐(ArN=PPh 2 )dibenzofuran were prepared. Two derivatives of this framework were studied, which differ in the steric demand of the N‐aryl group (Ar = Dipp, Mes). The ligand interacts with diethylzinc in solution but does not form a tightly bound complex, whereby the degree of association is found to be dependent on temperature. However, isolable complexes are formed upon reaction with the more Lewis acidic precursors ZnCl 2 and Zn(C 6 F 5 ) 2 . In this way, the ZnCl 2 complexes 1 and 2 and Zn(C 6 F 5 ) 2 complexes 3 and 4 were prepared and structurally characterized. The nuclearity of 1 and 2 was shown to depend on the bulk of the ligand. Furthermore, the strength of the bonding interaction between the zinc atoms and the dibenzofuran oxygen atoms in 3 and 4 also depends on the choice of ancillary ligand. Attempts to further derivatize these complexes were unsuccessful, and thus, functionalization of the complex LZnEt(OTf) was undertaken instead, resulting in formation of the novel linear trinuclear complex 5 .