The compounds [CH₂(6-t-Bu-4-Me-C₆H₂O)₂]PCl (1), (OCH₂CMe₂CH₂O)-PCl (2), and [ClPN(t-Bu)]₂ (3) have been utilized as precursors in the synthesis of (i) new pentacoordinate phosphorus compounds [e.g. CH₂(6-t-Bu-4-Me-C₆H₂O)₂ P(NRR′)(O₂C₆C1₄), CH₂(6-t-Bu-4-Me-C₆H₂O)₂PX[OC(O-i-Pr)N=N(C(O)O-i-Pr)],(ii) cyclic phosphates and their complexes [e.g. imidazolium⁺CH₂(6-t-Bu-4-Me-C₆H₂O)₂PO₂^-.MeOH], (iii) new cycloaddition products [e.g. CH₂(6-t-Bu-4-Me-C₆H₂O)₂PC(CO₂Me)C(CO₂Me)C(O)N, (iv) macrocyclic compounds [e.g. [(t-BuN)P]₂[-OCH₂CMe₂CH₂O-]_h2] and (v) phosphonates [e.g. (OCH₂CMe₂CH₂O)P (O)CH₂C(CN)=CHC₅H₄FeC₅H₅]. The synthetic and structural aspects of these new products are discussed.