Rhodium dinitriles

In particular, Fitzgerald s new route for the preparation of alkyl substituted dinitriles was used to prepare ethyl appended porphyrazines that were centrally metalated with iron and rhodium (Schemes 4 and 5). The main focus of Fitzgerald s work was on the magnetic and electronic properties of the metalated octaethylpor-... 

Wasserstoff durch eine Losung von (2,2 -Bi-pyridyl)-(l,5-hexadien)-rhodium-hexafluorophosphat und festem Natriumhydroxid in Methanol/Tetrahydrofuran leiten. Nach 30 min Hexandisaure-dinitril zugeben und das Gemisch bei 100° unter 1750 kPa WasserstofT-Druck 2h hydrieren Ausbeute 73%2. 

In einen Autoklaven 2%iges Rhodium auf Magnesiumoxid, Hexandisaure-dinitril, Tetrahydrofuran und fliissiges Ammoniak geben danach 3500 kPa WasserstofTaufdruckcn und 12 h auf 100° erhitzen Ausbeute 69% (Umsatz 74% mit 93% Selektivitat)3. 

This preparation illustrates the alkylation of malononitrile under acid-catalyzed conditions, and the use of diborane for the reduction of a dinitrile to a diamine. The procedure for the preparation of tert-butylmalononitrile has been outlined briefly by Boldt and co-workers.2 The generation of diborane in situ and the general method for nitrile reduction is that described by Brown and co-workers.3 Attempts to reduce the dinitrile to the diamine by other methods including catalytic hydrogenation (5% rhodium on alumina, 5 atm.), lithium aluminum hydride, and lithium aluminum hydride-aluminum chloride were singularly unsuccessful. 

The selective hydrogenation of aliphatic dinitriles to amino nitriles appears to be best accomplished using rhodium catalysts. Succinonitrile (45) was... 

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