Beschreibung:
<jats:title>Abstract</jats:title>
<jats:p>Homoleptic dinuclear lanthanide siloxide complexes [Ln(OSitBuPh<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>(μ-OSitBuPh<jats:sub>2</jats:sub>)]<jats:sub>2</jats:sub> (Ln = Y (<jats:bold>1a</jats:bold>), La (<jats:bold>1b</jats:bold>)), [Ln(OSiHtBu2)2(μ-OSiHtBu2)]2 (Ln = Y (<jats:bold>2a</jats:bold>), La (<jats:bold>2b</jats:bold>), Nd (<jats:bold>2c</jats:bold>), Lu (<jats:bold>2d</jats:bold>)), and {Ln[OSi(OtBu)<jats:sub>3</jats:sub>]<jats:sub>2</jats:sub>[μ-OSi(OtBu)<jats:sub>3</jats:sub>]}<jats:sub>2</jats:sub>(Ln = Y (<jats:bold>3a</jats:bold>), La (<jats:bold>3b</jats:bold>)) were synthesized according to the silylamide route in yields between 67 and 92%. Their bis(siloxide)-bridged molecular arrangement was proven by variable temperature <jats:sup>1</jats:sup>H NMR spectroscopy as well as by an Xray structure analysis of <jats:bold>2c</jats:bold>. The IR spectra of complexes <jats:bold>2</jats:bold>feature low-energy Si-H stretching vibrations (1965 - 1915 cm<jats:sup>−1</jats:sup>) indicative of β (Si-H)· · ·Ln agostic interactions. Complexes <jats:bold>2</jats:bold> and <jats:bold>3</jats:bold>readily form monomeric bis(donor) adducts with tetrahydrofurane, triphenylphosphine oxide, and N-methylimidazol as shown for fully characterized Ln(OSiHtBu<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub>(thf)<jats:sub>2</jats:sub> (Ln = Y (<jats:bold>4a</jats:bold>), La (<jats:bold>4b</jats:bold>)), Y(OSiHtBu<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub>(OPPh<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub> (<jats:bold>5</jats:bold>), Ln(OSiHtBu<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub>(N-MeIm)<jats:sub>2</jats:sub> (Ln = Y (<jats:bold>6a</jats:bold>), La (<jats:bold>6b</jats:bold>)), and Y[OSi(OtBu)<jats:sub>3</jats:sub>]<jats:sub>3</jats:sub>(thf)<jats:sub>2</jats:sub> (<jats:bold>7</jats:bold>). Treatment of complexes <jats:bold>1</jats:bold>- <jats:bold>3</jats:bold>with excess of trimethylaluminum (TMA) generated several alkylated rare-earth metal species including homoleptic Ln(AlMe<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub> as indicated by <jats:sup>1</jats:sup>H NMR spectroscopy. La[OSi(OtBu)<jats:sub>3</jats:sub>](AlMe<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>(AlMe<jats:sub>3</jats:sub>) (<jats:bold>8b</jats:bold>) was isolated by crystallization and analyzed by X-ray diffraction.</jats:p>