Acid-catalyzed cyclocondensations of 2-phosphanylanilines 1 with substituted benzaldehydes or heteroaryl aldehydes open a convenient route to new biaryl-type 1 H-1, 3- benzazaphosphole hybrid ligands 2a–f with o-phosphanylphenyl, pyridyl, imidazolyl, thienyl or o-methoxyphenyl donor groups (in addition to the σ 2 P donor) and to bromophenyl substituted benzazaphospholes 2g, h. Excess aldehyde leads to concomitant reductive N- ...