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Helberg, Julian; Oe, Yohei and Zipse, Hendrik (2018): Mechanistic Analysis and Characterization of Intermediates in the Phosphane-Catalyzed Oligomerization of Isocyanates. In: Chemistry-A European Journal, Vol. 24, No. 54: pp. 14387-14391

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The mechanism of the oligomerization of aliphatic isocyanates catalyzed by trialkylphosphanes has been studied through low temperature P-31 and N-15 NMR spectroscopy combined with computational chemistry. A revised mechanism is proposed that contains several (spiro)cyclic pentacoordinate phosphorous intermediates. Previously reported spectroscopic data of a transient intermediate has been reevaluated and assigned to a cyclic intermediate containing a P-N bond by experiments with N-15-labeled isocyanate. C-13, N-15, and P-31 NMR shifts that support this assignment have been calculated using quantum chemical methods.

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