Insertion of carbodiimides and organic azides into actinide - Carbon bonds
Organometallics, ISSN: 0276-7333, Vol: 28, Issue: 12, Page: 3350-3357
2009
- 94Citations
- 33Captures
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Article Description
Manipulation of steric crowding in organoactinide complexes has been explored by examining the insertion chemistry of carbodiimides, RN d C d NR, and organic azides, RN , with actinide alkyl, alkynyl, and aryl complexes. PrN d C d N Pr reacts with (C Me ) AnMe to produce the isomorphous methyl amidinates (C Me ) AnMe[( Pr)NC(Me)N( Pr)-κ N, N′], An) Th, 1; U, 2, in high yield. The reaction of PrN d C d N Pr with (C Me ) U(C t CPh) forms a similar insertion product, (C Me ) U(C t CPh)[( Pr)NC-(C t CPh)N( Pr)-κ N, N′], 3. (C Me ) U(C H ) does not generate an analogous product with PrN d C d N Pr, but forms instead a complex formally derived from carbodiimide insertion into a "(C Me ) U(C H )" intermediate, (C Me ) U[( Pr)NC d N( Pr)(C H )-κ N,κ C], 4. Adamantyl azide, AdN , inserts into the An - Me bonds in the (C Me ) AnMe complexes to make monomethyl actinide triazenido complexes that differ in the mode of triazenido coordination: (C Me ) ThMe[(Me)NN d N(Ad)- κ N ], 5, and (C Me ) UMe[(Me)NNN(Ad)-κ N ], 6. Aκ N -triazenido complex of thorium was also isolated in a crystal comprised of a mixture of (C Me ) ThMe[(Me)NNN(Ad)-κ N ] and (C Me ) Th(OH)[(Me)NNN(Ad)- κ N ], 7.
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