Unprecedented silicon(II)→calcium complexes with N-heterocyclic silylenes

The first N-heterocyclic silylene (NHSi) complexes of any s-block element to date are reported for calcium: [(η5-C5Me5)2Ca←:Si(O-C6H4-2-tBu){(NtBu)2CPh}] (6) and [(η5-C5Me5)2Ca←:Si(NtBuCH)2] (7). Complexes 6 and 7 are isolable in a facile way upon reaction of the corresponding free N-heterocyclic si...

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Hauptverfasser: Blom, Burgert (VerfasserIn) , Klatt, Günter (VerfasserIn) , Gallego, Daniel (VerfasserIn) , Tan, Gengwen (VerfasserIn) , Driess, Matthias (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 2015
In: Dalton transactions
Year: 2014, Jahrgang: 44, Heft: 2, Pages: 639-644
ISSN:1477-9234
DOI:10.1039/C4DT03148B
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C4DT03148B
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2015/dt/c4dt03148b
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Verfasserangaben:Burgert Blom, Günter Klatt, Daniel Gallego, Gengwen Tan and Matthias Driess

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520 |a The first N-heterocyclic silylene (NHSi) complexes of any s-block element to date are reported for calcium: [(η5-C5Me5)2Ca←:Si(O-C6H4-2-tBu){(NtBu)2CPh}] (6) and [(η5-C5Me5)2Ca←:Si(NtBuCH)2] (7). Complexes 6 and 7 are isolable in a facile way upon reaction of the corresponding free N-heterocyclic silylenes (NHSis) with [(η5-C5Me5)2Ca] (2). Complexes 6 and 7 were fully characterised by spectroscopic means and the single crystal X-ray diffraction analysis of 6 is also reported. Analysis of the bonding situation by DFT methods including a Bader Atoms in molecules (AIM) analysis is also reported. The bonding interaction between the Si and Ca centres in complexes 6 and 7 can best be viewed as σ-donor-acceptor interactions, with a considerable ionic contribution in the bond. The reactivity towards the oxygen containing substrates THF and benzophenone is also discussed. 
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