Three types of homo- and heterotrinuclear boron complexes have been obtained in moderate to good yields from reactions of salen-type ligands with boric acid and combinations of boric acid with phenylboronic and phenylphosphonic acid. The products are air-stable and have relatively high melting points (>290 degreesC) but are poorly soluble or insoluble in common organic solvents. They have been characterized as far as possible by elemental analysis, mass spectrometry, IR, H-1, B-11, and P-31 NMR spectroscopy, and X-ray crystallography. Furthermore, theoretical calculations have been performed for representative examples to permit a complete comparison of the different structure types. A detailed analysis of the molecular structures showed that the complexes are constructed around a central B3O3 or B2PO3 ring. The salen ligands are attached to two boron atoms of these rings, which have therefore tetrahedral coordination geometries. The complexes contain seven- and eight-membered heterocycles of the B2CnON2 (n = 2, 3) type with chair or twisted-chair and boat-chair or chair-chair conformations, respectively. In the homotrinuclear complexes one of the three boron atoms is three-coordinate and can therefore still act as Lewis acid, thus making these products interesting for catalytic applications, e.g. in asymmetric synthesis. Depending on the substitutents attached to the boron atoms, these complexes show a relationship with either trimetaboric acid, boroxine, or the tetraborate dianion found in Borax.