Homo- and heterochiral dimers (PHFX) 2, X = Cl, CN, CH 3, NC: To what extent do they differ?

Ab initio MP2/aug'-cc-pVTZ calculations have been performed to determine if intermolecular P-P distances, Z-P-P angles, binding energies, 31P chemical shieldings, or EOM-CCSD spin-spin coupling constants can differentiate between corresponding C 2 (homochiral) and C i (heterochiral) dimers (PHFX) 2, X = Cl, CN, CH 3, NC. With one exception, C i isomers have shorter P-P distances than corresponding C 2 isomers. Neither binding energies, Z-P-P angles, chemical shieldings, nor spin-spin coupling constants 1pJ(P-P) exhibit patterns which distinguish between corresponding C 2 and C i isomers. 1pJ(P-P) values correlate linearly with P-P distances, so that experimental values of 1pJ(P-P) could be used to extract intermolecular P-P distances. © 2012 Elsevier B.V. All rights reserved.