Herrmann Heike, Gehrmann Thorsten, Wadepohl Hubert, Gade Lutz H
Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Dalton Trans. 2008 Nov 28(44):6231-41. doi: 10.1039/b807808d. Epub 2008 Sep 30.
Reaction of the diamidozirconium complex [Zr(N2(TBS)Npy)(NMe2)2] (1) (N2(TBS)Npy = CH3C(C5H4N)(CH2NSiMe2tBu)2) or the diamidohafnium complex [Hf(N2(TBS)Npy)(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(N2(TBS)Npy)(=N-NC5H5)(OTf)(py)] (3) and [Hf(N2(TBS)Npy)(=N-NC5H5)(OTf)(py)] (4). These were converted to the acetylide complexes [Zr(N2(TBS)Npy)(=N-NC5H5)(CCPh)(py)] (5) and [Hf(N2(TBS)Npy)(=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(N2(TBS)Npy(OTf)(py)] (7-12) were formed instantaneously. A similar type of reaction with CO gave the isocyanato complex Zr(N2(TBS)Npy(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(N2(TBS)Npy)(=N-NC5H5)(OTf)]2 (14) and [Hf(N2(TBS)Npy)(=N-NC5H5)(OTf)]2 (15).
二氨基锆配合物[Zr(N2(TBS)Npy)(NMe2)2] (1)（N2(TBS)Npy = CH3C(C5H4N)(CH2NSiMe2tBu)2）或二氨基铪配合物[Hf(N2(TBS)Npy)(NMe2)2] (2)与一摩尔当量的1-氨基吡啶三氟甲磺酸盐在一当量吡啶存在下反应，生成相应的(1-吡啶鎓)亚氨基配合物[Zr(N2(TBS)Npy)(=N-NC5H5)(OTf)(py)] (3)和[Hf(N2(TBS)Npy)(=N-NC5H5)(OTf)(py)] (4)。通过与苯基乙炔锂反应并取代三氟甲磺酸根配体，这些配合物被转化为乙炔基配合物[Zr(N2(TBS)Npy)(=N-NC5H5)(CCPh)(py)] (5)和[Hf(N2(TBS)Npy)(=N-NC5H5)(CCPh)(py)] (6)。当3和4与一摩尔当量的R-NC（R = tBu、Cy、2,6-二甲基苯基）反应时，(1-吡啶鎓)亚氨基单元中的N-N键发生断裂，瞬间形成相应的碳二亚胺配合物M(N2(TBS)Npy(OTf)(py)] (7 - 12)。与CO进行的类似类型反应生成异氰酸根合配合物Zr(N2(TBS)Npy(OTf)(py)] (13)。最后，用B(C6F5)3脱去化合物3和4中的吡啶配体，导致形成三氟甲磺酸根桥连的双核配合物[Zr(N2(TBS)Npy)(=N-NC5H5)(OTf)]2 (14)和[Hf(N2(TBS)Npy)(=N-NC5H5)(OTf)]2 (15)。
