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Lookup NU author(s): Dr Keith Izod, Dr Corinne Wills, Emeritus Professor Bill CleggORCiD, Dr Ross Harrington
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The reaction between [[{Me2P(BH3)} (MOOC {(SiMe2)(CH2)}]Li(THF)(3)](2) and either Cp2Sn or Cp2Pb in toluene cleanly gives the compounds rac-[{Me2P(BH3)} (Me3Si)C {(SiMe2)(CH2)}](2)E in moderate yield [E = Sn (10), Pb (11)]. NMR spectra of crude samples indicate that 10 is predominantly formed as the rac isomer; for 11 there is no evidence for the formation of the meso diastereomer at all. Crystallization from diethyl ether yields the solvates 10 center dot Et2O and 11 center dot Et2O; X-ray crystallography reveals that these compounds crystallize as discrete rac-dialkylstannylene and -plumbylene species in which there are two short agostic-type B-H center dot center dot center dot E contacts. A DFT study suggests that these agostic-type interactions stabilize 10 and 11 by 47.7 and 42.7 kcal mol(-1), respectively. Calculations on the corresponding meso diastereomers; of 10 and 11 suggest that the tin and lead centers in these compounds have close contacts to just one hydrogen atom of a BH3 group, although a second, weaker B-H center dot center dot center dot E contact is observed in each case. These contacts afford an overall stabilization of 41.3 and 32.6 kcal mol(-1), respectively, for the meso-stannylene and -plumbylene.
Author(s): Izod K, Wills C, Clegg W, Harrington RW
Publication type: Article
Publication status: Published
Journal: Organometallics
Year: 2009
Volume: 28
Issue: 7
Pages: 2211-2217
ISSN (print): 0276-7333
ISSN (electronic): 1520-6041
Publisher: American Chemical Society
URL: http://dx.doi.org/10.1021/om801189h
DOI: 10.1021/om801189h
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