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Issue 44, 2008
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Zirconium and hafnium (1-pyridinio)imido complexes: functionalized terminal hydrazinediido analogues

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Abstract

Reaction of the diamidozirconium complex [Zr(N2TBSNpy)(NMe2)2] (1) (N2TBSNpy = CH3C(C5H4N)(CH2NSiMe2tBu)2) or the diamidohafnium complex [Hf(N2TBSNpy)(NMe2)2] (2) with one molar equiv. of 1-aminopyridinium triflate in the presence of one equiv. of pyridine gave the corresponding (1-pyridinio)imido complexes [Zr(N2TBSNpy)([double bond, length as m-dash]N–NC5H5)(OTf)(py)] (3) and [Hf(N2TBSNpy)([double bond, length as m-dash]N–NC5H5)(OTf)(py)] (4). These were converted to the acetylide complexes [Zr(N2TBSNpy)([double bond, length as m-dash]N–NC5H5)(CCPh)(py)] (5) and [Hf(N2TBSNpy)([double bond, length as m-dash]N–NC5H5)(CCPh)(py)] (6) by reaction with lithium phenylacetylide and substitution of the triflato ligand. Upon reaction of 3 and 4 with one molar equivalent of R-NC (R = tBu, Cy, 2,6-xyl), N–N bond cleavage in the (1-pyridinio)imido unit took place and the respective carbodiimido complexes [M(N2TBSNpy](N[double bond, length as m-dash]C[double bond, length as m-dash]NR)(OTf)(py)] (7–12) were formed instantaneously. A similar type of reaction with CO gave the isocyanato complex [Zr(N2TBSNpy](NCO)(OTf)(py)] (13). Finally, the abstraction of the pyridine ligand in compounds 3 and 4 with B(C6F5)3 led to the formation of the triflato-bridged dinuclear complexes [Zr(N2TBSNpy)([double bond, length as m-dash]N–NC5H5)(OTf)]2 (14) and [Hf(N2TBSNpy)([double bond, length as m-dash]N–NC5H5)(OTf)]2 (15).

Graphical abstract: Zirconium and hafnium (1-pyridinio)imido complexes: functionalized terminal hydrazinediido analogues

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Supplementary files

Article information


Submitted
08 May 2008
Accepted
31 Jul 2008
First published
30 Sep 2008

Dalton Trans., 2008, 6231-6241
Article type
Paper

Zirconium and hafnium (1-pyridinio)imido complexes: functionalized terminal hydrazinediido analogues

H. Herrmann, T. Gehrmann, H. Wadepohl and L. H. Gade, Dalton Trans., 2008, 6231
DOI: 10.1039/B807808D

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