ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Contributions to the Chemistry of Boron, LXII. N-Functional Substituted Aminohoranes : (Thiophosphorylamino)- and (Thiophosphinylamino)-diorgan ylboranesCompounds of the type R2P(S)—NR′—BR2″ (R=CH3, C6H5, (CH3)2N.—CH2(CH3N; R′ = CH3, C2H5, C6H5) are obtained a) by Si—N bond cleavage of R2P(S)—NR′—Si(CH3)3, b) by reaction of N-metallated thiophosphoryl- or thiophosphinylamines with diorganylboron halides, or c) by addition of sulfur to R2P—NR—BR2″. Si—N cleavage of silylamino-boranes by R2P(S)Cl predominantly yields borazines. As shown by n.m.r. investigations the barrier of rotation of the B—N bond decreased by introducing the R2P(S) group at the N atom of a monoaminoborane in accordance with the observed deshielding of the boron nucleus. This indicates a weakening at the B—N bond.
Notes:
Verbindungen des Typs R2P(S)—NR′—BR2″. (R=CH3, C6H5, (CH3)2N,—CH2(CH3)N; R′ = CH3, C2H5, C6H5) erhält man a) durch Silazanspaltung von R2P(S)—NR′—Si(CH3)3 und b) durch Umsetzung N-metallierter Thiophosphoryl- oder Thiophosphinylamine mit Diorganylborhalogeniden sowie c) durch Schwefeladdition an R2P—NR′—BR2″. Die Si—N-Spaltung von Silylaminoboranen durch R2P(S)Cl führt hingegen bevorzugt zu Borazinen. Wie die NMR-Spektren zeigen, senkt die Einführung der R2P(S)-Gruppe am N-Atom eines Aminoborans die Höhe der Rotationsbarriere um die B—N-Bindung in Übereinstimmnng mit dem beobachteten Abschirmungsverlust des B-Atoms. Dies zeigt eine Schwächung der B—N-Bindung an.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19731060517
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