A Cyclic Disilylated Stannylene: Synthesis, Dimerization, and Adduct Formation

Arp, Henning; Baumgartner, Judith; Marschner, Christoph; Müller, Thomas

doi:10.1021/ja1100883

Cited by 74 publications

(122 citation statements)

References 33 publications

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“…In the course of our studies concerning silyl-substituted tetrylenes we have recently reported the reactions of a 1,4-oligosilanyl dianion 20,21 with PbBr 2 , SnCl 2 , and GeCl 2 in the presence of PEt 3 to phosphine adducts of the respective cyclic plumbylene, 22 stannylene, 23 and germylene. 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 .…”

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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Section: Introductionmentioning

confidence: 99%

Coordination Chemistry of Disilylated Germylenes with Group 4 Metallocenes

et al. 2013

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“…6,7 These can be isolated either as the respective base adducts ( 1 and 2 ) or as dimers ( 3 and 4 ). The dimeric stannylene and plumbylene compounds 3 and 4 exhibit considerable structural differences.…”

Section: Introductionmentioning

confidence: 99%

Coordination Chemistry of Cyclic Disilylated Stannylenes and Plumbylenes to Group 4 Metallocenes

et al. 2012

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Reduction of group 4 metallocene dichlorides with magnesium in the presence of cyclic disilylated stannylene or plumbylene phosphine adducts yielded the respective metallocene tetrylene phosphine complexes. Under the same conditions the use of the respective dimerized stannylene or plumbylene gave metallocene ditetrylene complexes. A computational analysis of these reactions revealed for all investigated compounds multiple-bonded character for the M–E(II) linkage, which can be rationalized in the case of the monotetrylene complex with the classical σ-donor/π-acceptor interaction. The strength of the M–E(II) bond increases descending group 4 and decreases going from Sn to its heavier congener Pb. The weakness of the Ti–E(II) bonds is caused by the significantly reduced ability of the titanium atom for d–p π-back-bonding.

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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%