Quantum Chemical Calculations on CHOP Derivatives—Spanning the Chemical Space of Phosphinidenes, Phosphaketenes, Oxaphosphirenes, and COP− Isomers

Abstract

After many decades of intense research in low-coordinate phosphorus chemistry, the advent of Na[OCP] brought new stimuli to the field of CHOP isomers and derivatives thereof. The present theoretical study at the CCSD(T)/def2-TZVPP level describes the chemical space of CHOP isomers in terms of structures and potential energy surfaces, using oxaphosphirene as the starting point, but also covering substituted derivatives and COP− isomers. Bonding properties of the P–C, P–O, and C–O bonds in all neutral and anionic isomeric species are discussed on the basis of theoretical calculations using various bond strengths descriptors such as WBI and MBO, but also the Lagrangian kinetic energy density per electron as well as relaxed force constants. Ring strain energies of the superstrained 1H-oxaphosphirene and its barely strained oxaphosphirane-3-ylidene isomer were comparatively evaluated with homodesmotic and hyperhomodesmotic reactions. Furthermore, first time calculation of the ring strain energy of an anionic ring is described for the case of oxaphosphirenide.