A set of four pincer ligands, either the OCO type ligands L1–3 [2,6-(ROCH2)2C6H3]−, where R = Me (L1), mesityl (L2), t-Bu (L3) or novel NCO ligand [2-(Me2NCH2)-6-(t-BuOCH2)C6H3]− was studied. The reaction of L4Li with PCl3 resulted in isolation of [2-(OCH2)-6-(Me2NCH2)C6H3]PCl (1) as a result of intramolecular ether bond cleavage and elimination of t-BuCl. The conversion between the organolithium compounds L1,2,4Li and AsCl3 led to the desired chlorides, i.e.(L1)2AsCl (2), L2AsCl2 (3), L4AsCl2 (5), but an analogous reaction using the L3Li compound gave [2-(OCH2)-6-(t-BuOCH2)C6H3]AsCl (4) as a result of intramolecular cyclization. The organoantimony chloride L3SbCl2 was shown to undergo very slow cyclization in CDCl3 again via elimination of t-BuCl giving [2-(OCH2)-6-(t-BuOCH2)C6H3]SbCl (6) and it was demonstrated that this reaction may be accelerated by preparation of L3Sb(Cl)(OTf) (7) with more Lewis acidic central atom. On the contrary, both antimony derivatives of the NCO ligand L4, not only the chloride L4SbCl2 (8) but also the ionic pair containing highly Lewis acidic cation [L4SbCl]+[CB11H12]− (9), are stable without any indication for etheral bond cleavage. The situation is rather similar in the case of organobismuth derivatives of L4, which allowed isolation of compounds L4BiCl2 (10), L4Bi(Cl)(OTf) (11) and [L4BiCl]+[CB11H12]− (12). All studied compounds were characterized by the help of 1H and 13C NMR spectroscopy, ESI mass spectrometry, elemental analysis and (except 1) by single-crystal X-ray diffraction.