Past exam of the chemistry B course of the University of Cambridge 2022 Paper 2 B9 d Solution 2026-10-20
Three PO tetrahedra share corners in a ring. Each phosphorus has two ring-bridging oxygens and two terminal oxygens, sois one conventional Lewis representation of trimetaphosphate. Its three P and nine O atoms consist of three bridging and six terminal O atoms. Within each phosphate unit the two terminal bonds have delocalized character; drawing one P=O and one P–O is not a claim that every free anion has permanently different terminal oxygens.
A puckered six-membered P–O ring is expected. The tetrahedral phosphorus geometry and P–O–P torsional preferences allow folding without losing a required continuous perpendicular-p orbital system. This differs from the planar trigonal-boron arrangement. Tetrahedral P alone is not a geometrical proof of nonplanarity, since its two ring bonds could lie in a plane; the argument is that puckering is energetically accessible and relieves conformational strain without sacrificing a strong planar pi-conjugation benefit. The precise chair-like or boat-like distortion depends on environment and counterions.
Past exam of the chemistry B course of the University of Cambridge 2022 Paper 2 B9 e Solution 2026-10-20
A reasonable product is sodium facial trimetaphosphate–molybdenum tricarbonyl, with the anionOne terminal O from each phosphorus binds Mo; the three O donors occupy one octahedral face, while the three carbonyls occupy the opposite face. The ring bridges remain P–O–P bridges and are not replaced by Mo–P bonds. Mo remains Mo(0), , and electrons. Overall,acetonitrile can transiently replace CO during heating, but it is not required in the final six-coordinate proposal. The same anion has been structurally characterized with a different counterion: that primary study independently supports the facial O/CO connectivity, without establishing identical solubility or yield for the sodium salt.[ref]
Synthesis and characterization of the trimetaphosphate molybdenum tricarbonyl anion [(P3O9)Mo(CO)3]3- as its tris(bis(triphenylphosphine)iminium) salt by Christopher R. Clough and others. pp. 195–196, Scheme 2 and Fig. 1; §4.3 for Mo(CO)6 in refluxing acetonitrile