1255530-71-2Relevant academic research and scientific papers
Synthesis, characterisation and complexation of phosphino disilenes
Hartmann, Marco,Haji-Abdi, Abdishakur,Abersfelder, Kai,Haycock, Peter R.,White, Andrew J. P.,Scheschkewitz, David
, p. 9288 - 9295 (2010)
The treatment of disilenide Tip2SiSi(Tip)Li (1, Tip = 2,4,6-iPr3C6H2) with P-chloro phosphines affords the phosphino disilenes (2a-d; a: R = Ph, b: R = iPr, c: R = Cy, d: R = tBu), which were characterised by multinuclear NMR spectroscopy for 2a-d and a single crystal X-ray diffraction study in case of 2c. As an alternate synthetic method, the diphenyl derivative 2a could also be prepared by reaction of LiPPh2 with the thermally unstable iododisilene, Tip2Si=Si(Tip)I (3), which in turn was obtained by oxidation of 1 with stoichiometric amounts of iodine. Providing the first example for a SiSi bond with an iodo functionality, disilene 3 was fully characterised by multinuclear NMR and X-ray diffraction. The thermal rearrangement of phosphine disilene 2avia a C-H insertion reaction yields the diastereomeric mixture of a 1-phospha-2,3-disilaindane 4. The structure of the cis-diastereomer of 4 was determined by X-ray diffraction. Finally, the synthesis of first transition metal complex of 2a and 2b by their coordination to the [Pd(PCy3)] fragment is reported. The solid state structure of complex 5a reveals η2-coordination of the Si=Si bond of the phosphino disilene 2a with an intermediate bonding mode between π-complex and metallacyclopropane rather than coordination of the phosphino group. The Royal Society of Chemistry.
