Reactions of Unsaturated Nickel–Molybdenum and –Tungsten Complexes with Primary Amines: Chemoselective N-Coordination to Nickel To Give the First Structurally Characterised Primary Amine–Organonickel Complexes
✍ Scribed by Carmen Cuncillos Carmona; Sarah Clapham; Mathieu Gonidec; Vincent Ritleng; Pierre Braunstein; Richard Welter; Michael J. Chetcuti
- Publisher
- John Wiley and Sons
- Year
- 2010
- Tongue
- English
- Weight
- 475 KB
- Volume
- 2010
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
The reactions of selected primary amines with the unsaturatedheterodimetallic complex[(η-C 5 Me 5 )Ni(µ-CO)Mo(CO) 2 -(η-C 5 H 5 )](Ni-ត Mo) (1a) were investigated. Primary amines react with this heterodimetallic complex to form unstable adducts, which are in equilibrium with the free amine and complex 1a in solution. Complex 1b, the nickel-tungsten analogue of 1a, reacts similarly with benzylamine. The position of the equilibrium shifts in favour of the adducts at low temperature, and crystals of the allylamine and benzylamine complexes [(η-C 5 Me 5 )(RNH 2 )Ni-Mo(CO) 3 (η-C 5 H 5 )], (2a, R = C 3 H 5 ; 4a, R = PhCH 2 ) could be isolated. Their structures were established by single-crystal X-ray diffraction studies. The primary amines in complexes 2a and 4a are each coordinated, by means of their respective nitrogen atoms, to the nickel atom and thus provide the first structurally characterised examples of primary amine organometallic nickel complexes. The bonding of the amine to the heterodimetallic