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13 C and 31 P NMR spectra of 1‐adamantylphosphoryl derivatives
Author(s) -
Duddeck Helmut,
Hanna Atef G.
Publication year - 1985
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1260230112
Subject(s) - chemistry , chemical shift , electronegativity , atomic orbital , nmr spectra database , spectral line , interpretation (philosophy) , carbon 13 nmr , crystallography , stereochemistry , electron , organic chemistry , physics , nuclear physics , computer science , programming language , astronomy
The 13 C and 31 P NMR data of 26 bridgehead phosphorylated adamantanes, adamantyl‐P(O)XY, are reported. The 13 C chemical shifts of the α‐carbons are dependent on the X and/or Y group electronegativities, and can be interpreted by assuming p π d π electron back‐donation from X/Y to P. As expected, 31 P chemical shifts cannot be rationalized simply in similar terms. There is an extraordinarily good correlation between α‐carbon chemical shifts and the corresponding 1 J (CP) values. A tentative interpretation, based on the proportions of s and p character in phosphorus bond orbitals, is presented. Surprisingly large 4 J (PP) values were observed for two bis‐1,3‐dihalophosphophoryladamantanes.