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      Basic Reactivity Pattern of a Cyclic Disilylated Germylene

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          Abstract

          In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents. Reactions with the chalcogens sulfur, selenium, and tellurium led to dimers of the heavy ketone analogues. Reactions with water and ethyl bromide proceeded to give the respective oxidized germanol and germyl bromide. Two different reactions with alkynes were observed which led either to a germacyclopropene, by addition of tolane to the germylene, or to a silagermacyclobutene, likely formed by addition of the alkyne across a silagermene. Reaction via the silagermene was also observed in the reaction with benzophenone. Reaction of a germylene phosphine adduct with GeCl 2·(dioxane) provided insertion of the silylated germylene into a Ge–Cl bond, leading to a germylated chlorogermylene phosphine adduct.

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          An empirical correction for absorption anisotropy.

          A least-squares procedure is described for modeling an empirical transmission surface as sampled by multiple symmetry-equivalent and/or azimuth rotation-equivalent intensity measurements. The fitting functions are sums of real spherical harmonic functions of even order, ylm(-u0) + ylm(u1), 2 < or = l = 2n < or = 8. The arguments of the functions are the components of unit direction vectors, -u0 for the reverse incident beam and u1 for the scattered beam, referred to crystal-fixed Cartesian axes. The procedure has been checked by calculations against standard absorption test data.
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            Stable singlet carbenes as mimics for transition metal centers.

            This perspective summarizes recent results, which demonstrate that stable carbenes can activate small molecules (CO, H(2), NH(3) and P(4)) and stabilize highly reactive intermediates (main group elements in the zero oxidation state and paramagnetic species). These two tasks were previously exclusive for transition metal complexes.
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              Stable heavier carbene analogues.

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                Author and article information

                Journal
                Organometallics
                Organometallics
                om
                orgnd7
                Organometallics
                American Chemical Society
                0276-7333
                1520-6041
                03 August 2016
                22 August 2016
                : 35
                : 16
                : 2728-2737
                Affiliations
                []Institut für Anorganische Chemie, Technische Universität Graz , Stremayrgasse 9, 8010 Graz, Austria
                []Institut für Chemie, Universität Graz , Stremayrgasse 9, 8010 Graz, Austria
                [§ ]Institut für Chemie, Universität Oldenburg , Carl von Ossietzky-Strasse 1-3, 26211 Oldenburg, Federal Republic of Germany
                Author notes
                [* ]E-mail for J.B.: baumgartner@ 123456tugraz.at .
                Article
                10.1021/acs.organomet.6b00482
                4997532
                9f33a9c0-4e6d-424b-8243-983730b7ba6c
                Copyright © 2016 American Chemical Society

                This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

                History
                : 15 June 2016
                Categories
                Article
                Custom metadata
                om6b00482
                om-2016-00482h

                Inorganic & Bioinorganic chemistry
                Inorganic & Bioinorganic chemistry

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