Insertion reactions and catalytic hydrophosphination by triamidoamine-supported zirconium complexes
Organometallics, ISSN: 0276-7333, Vol: 29, Issue: 11, Page: 2557-2565
2010
- 79Citations
- 22Captures
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Article Description
Triamidoamine-supported zirconium phosphido complexes, (N N)ZrPRR′ (NN = N(CHCH NSiMe); R = alkyl, aryl; R′ = R, H), have been shown to catalyze the hydrophosphination of terminal alkynes as well as that of symmetric aryl and alkyl carbodiimides. A mechanism based on insertion of the substrate into the Zr-P bond is proposed on the basis of competition experiments and model examples of stoichiometric insertion reactions of polar, small-molecule substrates possessing C=O, C=N, C≡N, and C=S functionalities into the Zr-P bond. Molecular structures of the insertion products (NN)ZrN=C(PHCy)Ph (4), (NN)ZrN= C(PPh)Ph (5), and (NN)ZrPhNC(O)PPh (11), as well as (NN)Zr[(N,N)-(PrN) C(PPh)] (9), a key intermediate in the catalytic hydrophosphination of carbodiimides, have been determined. © 2010 American Chemical Society.
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