The hydrovinylation of styrene can be catalyzed by the addition of phosphane-modified Ni(II) compounds with high reactivity and enantioselectivity if the azaphospholene 1 is used as P-component of the catalysts. Until recently the industrial applications of 1 have been hampered by its difficult synthesis. To search for easier to synthesize, but equally well catalyzing derivatives of 1 a molecular modelling study was carried out. Based on already experimentally tested and structurally characterized azaphospholenes a model is developed, which not only leads to a better understanding of the catalytic process and but also to a relatively easy way to predict catalytic properties in these systems. Using an extended, customized valence force field several new derivatives of 1 have been tested. Their predicted and experimentally determined catalytic properties are in good agreement. The X-ray structures of the phenyl-substituted, monomeric azaphospholene 13, which hitherto results in the second best catalyst, and of its precursor 19 are presented.

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