Boron and Phosphorus Containing Heterosiliconoids: Stable p- and n-Doped Unsaturated Silicon Clusters
- 15 November 2019
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 141 (49), 19498-19504
- https://doi.org/10.1021/jacs.9b11181
Abstract
Unsaturated silicon clusters (siliconoids) are short-lived intermediates during the transition from molecules to the elemental bulk; stable representatives reiterate surface features of silicon materials. The incorporation of suitable heteroatoms into the cluster scaffold of stable siliconoids extends this analogy to the technological process of silicon doping. Here, we report boron- and phosphorus-containing heterosiliconoids with BSi5 and PSi5 core based on the global minimum Si6R6 platform (dubbed benzpolarene for its relationship to benzene). The reductive cleavage of an SiR2 moiety (R = 2,4,6-iPr3C6H2) from Si6R6 selectively yields a dianionic Si5R42− cluster as its lithium salt. Treatment with Me3SiCl affords the corresponding trimethylsilyl-substituted (Me3Si)2Si5R4. Reaction of Si5R42− with iPr2NECl2 (E = B, P) yields the unprecedented p- and n-doped heterosiliconoids iPr2NESi5R4. Their peculiar electronic features are compared to those of the hexasilabenzpolarene starting material on grounds of NMR spectroscopy, X-ray diffraction and DFT calculations.Funding Information
- Deutsche Forschungsgemeinschaft (DFG SCHE 906/4-1, DFG SCHE 906/4-2)
This publication has 65 references indexed in Scilit:
- Spirobis(pentagerma[1.1.1]propellane): A Stable TetraradicaloidJournal of the American Chemical Society, 2013
- Transition metal borylene complexesChemical Society Reviews, 2013
- Silicon electronics and beyondNature, 2011
- Bent phenyl groups in lithiosilanes—crystal structures and interpretation of this unanticipated featureChemical Communications, 2008
- Open, cyclic, and bicyclic compounds of double silylated phosphorus and boronDalton Transactions, 2004
- Reaction kinetics in silicon chemical vapor depositionCurrent Opinion in Solid State and Materials Science, 2002
- Aminophosphanes with bulky amino groups: Molecular structure, coupling constants 1J(31P, 15N) and 2J(31P, 29Si), and isotope‐induced chemical shifts 1Δ14/15N(31P)Heteroatom Chemistry, 2002
- Structural models of amorphous silicon surfacesPhysical Review B, 2001
- Synthesis and Temperature-Dependence of Hydrogen-Terminated Silicon ClustersThe Journal of Physical Chemistry B, 2001
- THE31P-CHEMICAL SHIFT OF DIPHOSPHENESPhosphorus, Sulfur, and Silicon and the Related Elements, 1997