Aminodiphenylphosphanes: Isotope-induced chemical shifts (1)Delta N-14/15(P-31), coupling constants (1)J(P-31, N-15), and chemical shifts delta N-15 and delta P-31
R. Contreras et al., Aminodiphenylphosphanes: Isotope-induced chemical shifts (1)Delta N-14/15(P-31), coupling constants (1)J(P-31, N-15), and chemical shifts delta N-15 and delta P-31, HETEROAT CH, 12(6), 2001, pp. 542-550
A series of aminodiphenylphosphanes 1 [Ph2P-N(H)tBu (a), -NEt2 (b), -NiPr2
(c)], 2 [Ph(2)PPi NHPh (a), -NH-2-pyridine (b), -NH-3-pyridine (c), -NH-4-p
yridine (d), NH-pyrimidine (e), NH-2,6-Me-2-C6H3 (f), NH-3-Me-2-pyridine (g
)], 3 [Ph2P-N(Me)Ph (a), -NPh2 (b)], and N-pyrrolyldiphenylphosphane 4 (Ph2
P-NC4H4) was prepared and studied by NMR (H-1, C-13, P-31 N-15 NMR) spectro
scopy. The isotope-induced chemical shifts (1)Delta N-14/15(P-31) were dete
rmined at natural abundance of N-15 by using HEED INEPT experiments. A depe
ndence of (1)Delta N-14/15(P-31) on the substituents at nitrogen was found
(alkyl < H < aryl; increasingly negative values). The magnitude and sign of
the coupling constants (1)J(P-31,N-15) (positive sign) are dominated by th
e presence of the lone pair of electrons at the phosphorus atom. The X-ray
structural analysis of 2b is reported, showing the presence of dieters owin
g to intermolecular hydrogen bridges in the solid state. (C) 2001 John Wile
y & Sons, Inc.