Table 1.

Experimental NMR parameters of nitrilium ions 10, 11 and related compounds (in CD₂Cl₂ at 305 K) and calculated bond energies (BDE) and fluoride ion affinity (FIA) of the corresponding silyl cation 2, 5, 9 and BCF (at M06‐2X/Def2‐TZVP, FIA at SCIPCM M06‐2X/Def2‐TZVP). Cpd=compound.

Cpd	Do	δ 19F	1 J(CF) [Hz]	1 J(SiDo) [Hz]	FIA [kJ mol−1]	BDE (Si−N) [kJ mol−1]
10 a	OPh	−87.9	269.1	–	215	96
10 b	SPh	−94.3	264.1	–	182	70
10 c	SePh	−98.5	260.2	33	176	65
10 d	TeMes	−102.1	257.1	171	171	51
10 e	Br	−87.6[b]	269.7	–	235	119
10 f	I	−90.9[b]	266.7	–	222	105
11 a	OPh	−90.2[a]	267.7[a]}	–	201	90
11 c	SePh	−101.9	257.2	56	167	62
11 e	Br	−88.0[b]	269.1	–	224	112
4	–	−92.5	268.0	–	–	–
6	–	−86.6	272.8	–	302	183
FBN	–	−103.4	255.7	–	–	–

[a] At 233 K in CD₂Cl₂vs. reference at 233 K δ ¹⁹F=−162.87, see Supporting Information. [b] Broad signals: [FWHH=299 Hz (10 e); 347 Hz (10 f); 109 Hz (11 e)].