Cyclic Disilylated and Digermylated Germylenes

Most known silatrane chemistry is concerned with examples where the attached silatrane substituent atom is that of an element more electronegative than silicon. The current study features silylated silatranes with a range of electropositive elements attached to the silyl group. The resulting compounds show different degrees of electron density on the silatrane-substituted silicon atom. This directly affects the Si–N interaction of the silatrane which can be monitored either by 29Si NMR spectroscopy or directly by single crystal XRD analysis of the Si–N distance. Within the sample of study the Si–N distance is increased from 2.153 to 3.13 Å. Moreover, the bis(trimethylsilyl)silatranylsilyl unit was studied as a substituent for disilylated germylene adducts.

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“…As was observed before for other NHC-stabilized germylenes, 44−48 adduct 10 is stable and does not show any tendency to rearrange to 9 .…”

Section: Resultssupporting

confidence: 81%

Tuning the Si–N Interaction in Metalated Oligosilanylsilatranes

et al. 2017

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“…24 In a subsequent contribution we demonstrated that the dimeric forms of these plumbylene and stannylene but also the respective PEt 3 adducts could be used to obtain group 4 metallocene plumbylene and stannylene complexes I and II . 25 …”

Section: Introductionmentioning

confidence: 94%

“…With the recent availability of germylene phosphine adducts 24 the question arose whether the addition of disilylated germylenes to group 4 metallocenes would lead to the respective germylene or digermene complexes.…”

Section: Introductionmentioning

confidence: 99%

Coordination Chemistry of Disilylated Germylenes with Group 4 Metallocenes

et al. 2013

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Reaction of the PEt3 adduct of a disilylated five-membered cyclic germylene with group 4 metallocene dichlorides in the presence of magnesium led to the formation of the respective germylene metallocene phosphine complexes of titanium, zirconium, and hafnium. Attempts to react the related NHC adduct of a disilylated four-membered cyclic germylene under the same conditions with Cp2TiCl2 did not give the expected germylene NHC titanocene complex. This complex was, however, obtained in the reaction of Cp2Ti(btmsa) with the NHC germylene adduct. A computational analysis of the structure of the group 4 metallocene germylene complexes revealed the multiple-bond character of the M–Ge(II) linkage, which can be rationalized with the classical σ-donor/π-acceptor interaction. The strength of the M–Ge(II) bond increases descending group 4.

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“…The halogenated silicon is kinetically protected by the sterical demand of the vicinal trimethylsilyl groups. While this environment has a stabilizing effect on the molecule [30,31], it also makes derivatization reactions more difficult. However, it was possible to synthesize the cyclopentasilane as well as the difluoro-, dichloro-, dibromo-, and diiodo-derivatives via one or two-step reaction procedures (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The stability of Kira's silylene is caused by sterically demanding trimethylsilyl-groups on the carbons in a,a'-position. The same protective groups have been used for the generation of germylenes, stannylenes and plumbylenes with only silicon atoms in the ring backbone [30,31].…”

Section: Introductionmentioning

confidence: 99%