Diane Dickie - Structures and CO2 Reactivity of Zinc Complexes of Bis(diisopropyl-) and Bis(diphenylphosphino)amines.

Document created by Diane Dickie on Nov 17, 2015
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  Dickie, Diane A., Kemp, Richard A. Organometallics  33 (22) 6511-6518

  Abstract: The bis(phosphino)amines (R2P)NH(PR'2)   (R = R' = isopropyl; R = R' = phenyl; R = iso-Pr, R' = phenyl)   react with ZnEt2 to form complexes with two different structural   motifs, either the homoleptic monomeric P,P-chelates   Zn[N(i-Pr2P)2]2 and Zn[N(i-Pr2P)(Ph2P)]2 or the heteroleptic   dimeric Zn2N2P2 heterocycles {EtZn[N(PPh2)2]}2 and   {EtZn[N(PPh2)(i-Pr2P)]}2. In two cases, CO2 reacts with these   complexes to give adducts Zn[O2CP(i-Pr2)NP(i-Pr2)]2 and   Zn[O2CP(i-Pr2)NPPh2][Ph2PN(i-Pr2P)]ZnEt2, similar to adducts   formed from the reaction of CO2 with frustrated Lewis pairs   (FLPs). In the other two cases, reaction with CO2 results in   cleavage and rearrangement of the N-P bonds to give either   N(PPh2)3 or Ph2P(iPr2P)NPPh2. The Zn complexes and their CO2   products were characterized with a combination of single crystal   x-ray diffraction and multinuclear NMR spectroscopy. [on   SciFinder(R)]

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