Toggle Main Menu Toggle Search

Open Access padlockePrints

Seven-Membered Cyclic Dialkylstannylene and -Plumbylene Compounds Stabilized by Agostic-type B-H center dot center dot center dot E Interactions [E = Sn, Pb]

Lookup NU author(s): Dr Keith Izod, Dr Corinne Wills, Emeritus Professor Bill Clegg, Dr Ross Harrington

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


Abstract

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.


Publication metadata

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


Altmetrics

Altmetrics provided by Altmetric


Actions

Find at Newcastle University icon    Link to this publication


Share