ISSN:
0044-2313
Keywords:
1,2-Diphospha-3,4-diboretanes
;
1,3-diphospha-2,4,5-triborolane derivative
;
preparation
;
molecular structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
1,2-Diphospha-3,4-diboretanes and 1,3-Diphospha-2,4,5-triborolane: Synthesis and Structure as well as Calculations on the Molecular Structure On the Effect of Substituents on the Structure of 1,2-Diphospha-3,4-diboretane[2 + 2]-Cyclocondensation reactions led to the synthesis of the 1,2-diphospha-3,4-diboretanes [(t-BuP)2B2(NMe2)2], 1 a, and [(t-BuP)2B(NMe2)B(NiPr2)], 1 b. Their molecular structures have been determined by X-ray methods, and these are compared with the structure of [(t-Bu)P—BN(iPr2)]2, 2 a. Compounds 1 show a folded B2P2 four membered ring having tert.-butyl groups in anti-positions. Ab initio calculations on 1,2-diphospha-3,4-diboretanes demonstrate that two conformers with anti-orientation of the substituents at the phosphorus atoms can be expected. These differ by the relative orientation of the almost planar P2BR groups to the BP2 plane. The influence of substituents (H and NH2 at the B atoms, and H and Me at the P atoms) on the ring conformation has been studied. Finally, the first derivative of a 1,3-diphospha-2,4,5-triborolane, 3 a, is reported.
Notes:
Durch [2 + 2]-Cyclokondensationen wurden die 1,2-Diphospha-3,4-diboretane [(t-BuP)2B2(NMe2)2], 1 a, und [(t-BuP)2B(NMe2)B(NiPr2)], 1 b, dargestellt, ihre Molekülstrukturen mit Röntgenbeugungsmethoden bestimmt und mit der Struktur von [(t-Bu)P—B(NiPr2)]2, 2 a, verglichen. In den Verbindungen 1 liegen gefaltete B2P2-Vierringe vor mit anti-ständigen tert.-Butylgruppen, während das Ringsystem in 2 a planar gebaut ist, die tert.-Butylgruppen aber ebenfalls anti-Stellung einnehmen. Ab initio-Rechnungen an 1,2-Diphospha-3,4-diboretanen belegen, daß zwei unterschiedliche Konformere mit anti-Orientierung der Substituenten an den P-Atomen stabil sind, die sich durch die relative Orientierung der annähernd trigonal-planaren P2BR-Baugruppen zur BP2-Ebene voneinander unterscheiden. Der Einfluß von Substituenten (H und NH2 am B-Atom, H und CH3 am P-Atom) wird ermittelt. Beschrieben wird ferner das erste Derivat eines 1,3-Diphospha-2,4,5-triborolans, 3 a.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19956210702
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