Phosphaboranes and carbaphosphaboranes

The electronic structure of 1,2-PCB10H11 molecular films: a precursor to a novel semiconductor

“…The HOMO-LUMO gap center is offset with respect to the Fermi level differently for the two molecules by more than 3 to 4 eV, that is to say that the Fermi level is placed some 3 to 4 eV closer to the low est unoccupied (LUMO) band edge for 1,2-PCB 10 H 11 than is the case for 1,2-C 2 B 10 H 12 . In this regard, 1,2-PCB 10 H 11 more closely resembles 1,7-C 2 B 10 H 12 [7,19,20] and C 60 where the Fermi energy lies just below the LUMO (the conduction band minimum) [43][44][45]. Without knowing the majority car rier, we believe these results suggest that 1,2-PCB 10 H 11 forms a molecular semiconducting thin fi lm that is strongly n-type compared to the slightly p-type and insulating 1,2-C 2 B 10 H 12 molecular fi lms.…”

“…1,2-PCB 10 H 11 was prepared in 41% yield by the method of Little and Todd from the reaction of Na 3 [CB 10 H 11 ]and PCl 3 [19,20]. The resultant pale yellow powder was sublimed at 100 °C and 0.…”

Main-group Heteroboranes

“…The first polyhedral phosphaborane was obtained by reaction o f [B n H 13 ] 2~ with PhPCl 2 to give closo-PhPB n H u in low yield after an extensive purification procedure. 69 71 The derivative c/os0-6-Et 3 N-2-PB 9 H 8 was isolated from this type o f reaction. An x-ray structure study o f this compound as an enantiomeric mixture has been reported.…”

Synthesis and Characterisation of Sigma‐ and Pi‐Bonded Metallaphosphacarboranes

“…1, 2‐ closo ‐CPB 10 H 11 was first reported by Todd in 1967, and was isolated from the reaction of Na 3 [7‐ nido ‐CB 10 H 11 ]·(THF) 2 with PCl 3 9. It can be thermally isomerised to the 1, 7‐ and then to the 1, 12‐isomer, and like the diphospha‐ and diarsaborane analogues, a boron atom can be removed with piperidine 10.…”