We use cookies to ensure that we give you the best experience on our website. By continuing to browse this repository, you give consent for essential cookies to be used. You can read more about our Privacy and Cookie Policy.

Durham e-Theses
You are in:

Alkylideneamino derivatives of some main group elements

Snaith, R. (1971) Alkylideneamino derivatives of some main group elements. Doctoral thesis, Durham University.



This thesis describes the preparation of some alkylideneamino derivatives containing groups R(_2)C:N-attached to lithium, boron, aluminium, gallium, silicon and phosphorus, compounds which were prepared with the object of finding model systems for the study of dative N=M-bonding between nitrogen and these elements. Systems in which R = (^t)Bu proved particularly apt for this purpose. The new compounds di-t-butylmethyleneamine, (^t)BU(_2)C:NH, and its N-lithio and N-trimethylsilyl derivatives, (^t)BU(_2)C:NLi and (^t)Bu(_2)C:NSiMe(_3), were prepared (Chapter I) and used to synthesise di-t-butylmethyleneamino-boranes (Chapter III), -alanes (Chapter IV) and -silanes (Chapter VI), The infrared and (^1)H n.m.r. spectra of the boranes ((^t)Bu(_2)C:N)(_x)BX(_3-x) were consistent with allene-like geometries for these compounds, with the linear C=N=tB skeletons appropriate for significant (p → p) π-interaction between nitrogen and boron. Similar (p →p) and also (p →d) N=Al it-interactions were detected spectroscopically in 3- and 4-co-ordinate aluminium derivatives, and (p →d) N Si n-bonding was apparently indicated by the spectra of some di-t-butylmethyleneaminosilanes, (^t)Bu(_2)C:NSiR(_n)Cl(_3-n). Such interactions have subsequently been confirmed by X-ray crystallographic work on one boron and one aluminium compound. Studies on tetramethylguanidine adducts, (Me(_2)N)(_2)C:NH,AlX(_3) and on derivatives [(Me(_2)N)(_2)C:NAlX(_2)](_2) (X = Et, CI) (Chapter V) showed them to contain only single Al-N bonds, and apparently four-co-ordinate aluminium in each case. The spectroscopic effects of co-ordination of either a proton or boron trifluoride to various alkylideneamines R(^1)R(^2)C:NH, needed as reference systems for interpreting the spectra of derivatives R(^1)R(^2)C:NMX(_n), are described in Chapter II.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1971
Copyright:Copyright of this thesis is held by the author
Deposited On:13 Nov 2013 15:39

Social bookmarking: del.icio.usConnoteaBibSonomyCiteULikeFacebookTwitter