ISSN:
0044-2313
Keywords:
Diphosphane-borane
;
Triphosphane-2-borane
;
Triphosphane-1,3-bis(borane)
;
Sodium-1,1,2-tris(borane)-1,2,2-trihydrogendiphosphide
;
Diphosphane(4)
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Contributions to the Chemistry of Phosphorus. 240. On the Reactive Behaviour of Diphosphane-borane, P2H4 · BH3Under mild temperature conditions, the thermal decomposition of diphosphane-borane (1) gives rise to the formation of phosphane-borane, PH3 · BH3, and triphosphane-2-borane, PH2—PH(BH3)—PH2 (2). In the presence of diphosphane-1,2-bis(borane), triphosphane-1,3-bis(borane), BH3—PH2—PH—PH2—BH3 (3), is formed additionally. The thermolysis product at room temperature is a polymeric solid of varying composition which contains phosphorus, boron, and hydrogen.Compound 1 reacts with metalating agents such as n-BuLi, LiBH4, and NaBH4 to furnish the borane-trihydrogendiphosphide ion, [PH2—PH—BH3]-, which immediately disproportionates to give the corresponding mono-and triphosphane derivatives. In the presence of an excess of THF-borane and in the case of a 1 : 1 molar ratio of 1 : NaBH4, the disproportionation does not occur and the new diphosphide derivative sodium-1,1,2-tris(borane)-1,2,2-trihydrogendiphosphide, Na[(BH3)2PH—PH2BH3] (4) can be obtained. The action of additional NaBH4 yields the diphosphide dianion with four coordinated BH3 groups.
Notes:
Die thermische Zersetzung von Diphosphanboran (1) führt unter milden Temperaturbedingungen zur Bildung von Phosphan-boran, PH3 · BH3, und Triphosphan-2-boran, PH2—PH(BH3)—PH2 (2). In Gegenwart von Diphosphan-1,2-bis(boran) entsteht zusätzlich Triphosphan-1,3-bis-(boran), BH3—PH2—PH—PH2—BH3 (3). Bei Raumtemperatur wird ein polymerer Feststoff gebildet, der Phosphor, Bor und Wasserstoff in wechselnder Zusammensetzung enthält.Die Verbindung 1 reagiert mit Metallierungsmitteln, wie n-BuLi, LiBH4 und NaBH4, zum Boran-trihydrogendiphosphid-Ion, [PH2—PH—BH3]-, das sofort zu entsprechenden Mono- und Triphosphanderivaten disproportioniert. Bei Anwesenheit von überschüssigem THF-Boran und Reaktion im Molverhältnis 1 : NaBH4 = 1 : 1 kann die Disproportionierung verhindert und das neue Diphosphidderivat Natrium-1,1,2-tris-(boran)-1,2,2-trihydrogendiphosphid, Na[(BH3)2PH—PH2BH3] (4), gewonnen werden. Mit weiterem NaBH4 entsteht das Diphosphid-Dianion mit vier koordinierten BH3-Gruppen.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966221207
Permalink
