Oxidative addition versus substitution reactions of group 14 dialkylamino metalylenes with pentafluoropyridine.
Dialkylamino compounds of group 14 elements (Si, Ge, Sn) in the +2 oxidation state supported by benzamidinate ligands were synthesized and treated with pentafluoropyridine. Two different modes of reactivity were observed, depending on the metal atom and the basicity of the substituent at the metal. Pentafluoropyridine undergoes oxidative addition reaction at the Si(II) and Ge(II) atoms whereas at the Sn(II) atom substitution of the NMe(2) group by the para fluorine of pentafluoropyridine occurs. The C-F bond activation by the lone pair of germanium is the first report of this kind. The Sn(II) fluoride obtained has an elongated Sn-F bond length and can be used as a good fluorinating agent. The compounds were characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray structural analysis. Single crystal X-ray structural analysis of the tin fluoride shows an asymmetric dimer with weak [Formula: see text] interactions.
Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, D-37077, Göttingen, Germany.
Prinson P
PP
Samuel
Amit Pratap
AP
Singh
Sankaranarayana Pillai
SP
Sarish
Julia
J
Matussek
Ina
I
Objartel
Herbert W
HW
Roesky
Dietmar
D
Stalke
D000588:Amines / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005857:Germanium / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry*; D014001:Tin / Q000737:chemistry*; D005466:Fluorocarbons
D000588:Amines; D005857:Germanium; D011725:Pyridines; D012825:Silicon; D014001:Tin; C486857:pentafluoropyridine; D005466:Fluorocarbons