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Reductions of these with a magnesium(I) dimer, {(<jats:sup>Mes<\/jats:sup>Nacnac)Mg}<jats:sub>2<\/jats:sub> (<jats:sup>Mes<\/jats:sup>Nacnac=[(MesNCMe)<jats:sub>2<\/jats:sub>CH]<jats:sup>\u2212<\/jats:sup>, Mes=mesityl), afforded singly bonded amido\u2010digermynes (<jats:sup>TBo<\/jats:sup>LGe\u2212Ge<jats:sup>TBo<\/jats:sup>L and <jats:sup>PhBo<\/jats:sup>LGe\u2212Ge<jats:sup>PhBo<\/jats:sup>L), and an amido\u2010distannyne (<jats:sup>PhBo<\/jats:sup>LSn\u2212Sn<jats:sup>PhBo<\/jats:sup>L), in addition to several low\u2010valent, amido stabilized tetrel\u2013tetrel bonded cluster compounds, (<jats:sup>DBu<\/jats:sup>LGe)<jats:sub>4<\/jats:sub>, (<jats:sup>DBu<\/jats:sup>LSn)<jats:sub>6<\/jats:sub> and Sn<jats:sub>5<\/jats:sub>(<jats:sup>TBo<\/jats:sup>L)<jats:sub>4<\/jats:sub>. The nature of the products resulting from these reactions was largely dependent on the steric bulk of the amide ligand employed. Cluster (<jats:sup>DBu<\/jats:sup>LGe)<jats:sub>4<\/jats:sub> possessed an unusual folded butterfly structure, the bonding and electronic of which were examined using DFT calculations. Reactions of the amido\u2010germanium(I) compounds with H<jats:sub>2<\/jats:sub> were explored, and gave rise to the amido\u2010digermene, <jats:sup>TBo<\/jats:sup>L(H)Ge=Ge(H)<jats:sup>TBo<\/jats:sup>L and the cyclotetragermane, {<jats:sup>DBu<\/jats:sup>L(H)Ge}<jats:sub>4<\/jats:sub>. Reactions of (<jats:sup>DBu<\/jats:sup>LGe)<jats:sub>4<\/jats:sub> with a series of unsaturated small molecule substrates yielded <jats:sup>DBu<\/jats:sup>LGeOGe<jats:sup>DBu<\/jats:sup>L, <jats:sup>DBu<\/jats:sup>LGe(\u03bc\u2010C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub>Ge<jats:sup>DBu<\/jats:sup>L and <jats:sup>DBu<\/jats:sup>LGe(\u03bc\u20101,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>8<\/jats:sub>)(\u03bc\u20101,2\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>8<\/jats:sub>)Ge<jats:sup>DBu<\/jats:sup>L. The latter results imply that (<jats:sup>DBu<\/jats:sup>LGe)<jats:sub>4<\/jats:sub> can act as a masked source of the digermyne <jats:sup>DBu<\/jats:sup>LGeGe<jats:sup>DBu<\/jats:sup>L in these reactions. All further reactivity studies indicated that the germanium(I) compounds exhibit a \u201ctransition\u2010metal\u2010like\u201d behavior, which is closely related to that previously described for bulky digermynes and related compounds.<\/jats:p>","DOI":"10.1002\/chem.201804770","type":"journal-article","created":{"date-parts":[[2018,10,29]],"date-time":"2018-10-29T06:50:23Z","timestamp":1540795823000},"page":"2773-2785","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":61,"title":["Synthesis and Reactivity Studies of Amido\u2010Substituted Germanium(I)\/Tin(I) Dimers and Clusters"],"prefix":"10.1002","volume":"25","author":[{"given":"John A.","family":"Kelly","sequence":"first","affiliation":[{"name":"Monash Centre for Catalysis School of Chemistry Monash University  PO Box 23 Melbourne VIC, 3800 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