Dispersion Energy Enforced Dimerization of a Cyclic Disilylated Plumbylene

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

doi:10.1021/ja300654t

Cited by 81 publications

(102 citation statements)

References 40 publications

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“…While we initially expected these compounds to exhibit a chemical behavior similar to that of the acyclic analogues, it turned out that the cyclic nature renders the tetrylene atom more accessible so that dimerization becomes a more facile process. 12,13 …”

Section: Introductionmentioning

confidence: 99%

Cyclic Disilylated and Digermylated Germylenes

et al. 2013

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The preparation of triethylphosphine adducts of cyclic disilylated or digermylated germylenes was achieved by reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with GeBr2·(dioxane) and PEt3. Phosphine abstraction with B(C6F5)3 allowed formation of the base-free germylenes, which undergo 1,2-trimethylsilyl shifts to the germylene atom to form the respective silagermene or digermene, which further dimerize in [2 + 2] cycloadditions to tricyclic compounds. The reasons responsible for the germylenes’ completely different reactivities in comparison to the previously studied analogous stannylenes and plumbylenes were elucidated in a theoretical study.

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Section: Introductionmentioning

confidence: 99%

Cyclic Disilylated and Digermylated Germylenes

et al. 2013

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“…2,3 Recently, we started some investigations concerning the chemistry of cyclic bis(silyl)-substituted germylenes, 4 stannylenes, 5 and plumbylenes. 6 Addition of the strong donor molecule PEt 3 allowed us to successfully trap the cyclic stannylene, which undergoes dimerization as a free species, as the respective adduct 1 . 5 This compound and the respective plumbylene adduct could be used for studying their coordination chemistry with group 4 metallocenes.…”

Section: Introductionmentioning

confidence: 99%

Coordination Chemistry of Disilylated Stannylenes with Group 10 d¹⁰Transition Metals: Silastannene vs Stannylene Complexation

et al. 2013

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The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners. While with nickel stannylene complex formation was observed, coordination of the stannylenes to palladium and platinum compounds led to unusual silastannene complexes of these metals. A computational model study indicated that in each case metal stannylene complexes were formed first and that the disilylstannylene/silastannene rearrangement occurs only after complexation to the group 10 metal. The isomerization is a two-step process with relatively small barriers, suggesting a thermodynamic control of product formation. In addition, the results of the computational investigation revealed a subtle balance of steric and electronic effects, which determines the relative stability of the metalastannylene complex relative to its silastannene isomer. In the case of cyclic disilylstannylenes, the Pd(0) and Pt(0) silastannene complexes are found to be more stable, while with acyclic disilylstannylenes the Ni(0) stannylene complex is formed preferentially.

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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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Dispersion Energy Enforced Dimerization of a Cyclic Disilylated Plumbylene

Cited by 81 publications

References 40 publications

Cyclic Disilylated and Digermylated Germylenes

Cyclic Disilylated and Digermylated Germylenes

Coordination Chemistry of Disilylated Stannylenes with Group 10 d¹⁰Transition Metals: Silastannene vs Stannylene Complexation

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

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Dispersion Energy Enforced Dimerization of a Cyclic Disilylated Plumbylene

Cited by 81 publications

References 40 publications

Cyclic Disilylated and Digermylated Germylenes

Cyclic Disilylated and Digermylated Germylenes

Coordination Chemistry of Disilylated Stannylenes with Group 10 d10Transition Metals: Silastannene vs Stannylene Complexation

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

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Coordination Chemistry of Disilylated Stannylenes with Group 10 d¹⁰Transition Metals: Silastannene vs Stannylene Complexation