Published in:
Chemistry – A European Journal, 25 (2019) 59, Seite 13509-13513
Language:
English
DOI:
10.1002/chem.201903676
ISSN:
1521-3765;
0947-6539
Origination:
Footnote:
Description:
<jats:title>Abstract</jats:title><jats:p>The first unsupported barium siloxide, the homoleptic dimer [Ba<jats:sub>2</jats:sub>{μ<jats:sub>2</jats:sub>‐OSi(SiMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>}<jats:sub>3</jats:sub>{OSi(SiMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>}], is presented, and its structural features are discussed in the light of DFT computations. This complex, together with the related [Ba{μ<jats:sub>2</jats:sub>‐OSi(SiMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>}{N(SiMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>}]<jats:sub>2</jats:sub> and their parent [Ba{N(SiMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>}<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub>, mediates the formation of asymmetric siloxanes R<jats:sub>3</jats:sub>Si−O−SiR′<jats:sub>3</jats:sub> through the first case of main group metal‐mediated dehydrocoupling of silanols and hydrosilanes. Early kinetic analysis highlights an unusual catalytic manifold.</jats:p>