Table 4.

Scaled (using PH₃ and PCl₃) chemical shifts for the “failures” 1a, 8, and 32 for various optimization and NMR functionals.

Entry	Optimization	NMRa	1a PA	1a PB	8 PB	32	MADb
	experimental		39.6	297.6	−157.7	−181
1	PBE0 (Latypov)	PBE0 (Latypov)	37.2	282.5	−139.6	−112.7	33.9
2	B3LYP	B3LYP	42.1	278.4	−114.2	−59.2	61.5
3	M06-2X	B3LYP	40.3	272.2	−125.7	−167.9	23.5
4	M06-2X	M06-2X	56.2	336.0	−115.1	−175.2	28.9
5	M06-2X	TPSSTPSS	36.9	256.4	−135.8	−164.1	26.7
6	M06-2X	TPSSTPSS*	34.3	260.3	−148.1	−173.3	18.2
7	TPSSTPSS	TPSSTPSS*	31.8	259.0	−132.9	−20.9	74.5
8	M06-2X	LC-TPSSTPSS	38.1	339.4	−132.4	−184.8	23.6
9	M06-2X	LC-TPSSTPSS*	33.4	345.0	−149.8	−199.0	24.4
10	M06-2X	PBETPSS	44.1	260.1	−124.5	−152.2	33.1
11	M06-2X	PBETPSS*	41.4	264.4	−139.0	−162.3	23.5
12	M06-2X	LC-PBETPSS	40.9	342.1	−127.4	−178.4	25.8
13	M06-2X	LC-PBETPSS*	35.0	348.7	−147.5	−195.4	25.3
14	M06-2X	M06-L	36.5	274.4	−156.7	−180.9	8.1
15	M06-2X	M06-L*	32.1	278.1	−171.5	−190.8	14.4
16	M06-L	M06-L	27.4	257.4	−161.4	−61.5	54.5
17	M06-2X	M11-L	23.6	231.5	−156.5	−181.8	22.7
18	M11-L	M11-L	7.8	212.3	−172.6	−70.1	70.4
19	M11	M11	43.8	339.8	−124.9	−194.4	29.5
20	MN12-SX	MN12-SX	27.2	274.6	−154.9	−145.6	20.4
21	BLYP-D3	BLYP-D3	34.4	242.3	−100.1	−7.6	95.4
22	M06-2X-D3	M06-2X-D3	56.1	336.0	−115.0	−175.2	29.0
23	M06-L-D3	M06-L-D3	27.3	257.4	−161.3	−61.5	54.4
24	TPSSTPSS-D3	TPSSTPSS-D3*	31.8	259.6	−140.5	−23.1	71.0
25	M06-2X	ωB97X-D	39.3	293.1	−132.8	−177.7	10.9
26	ωB97X-D	ωB97X-D	38.0	292.8	−136.9	−174.2	10.8
27	M06-2X	PBE0	43.3	285.1	−133.2	−169.0	16.3

^aCSGT method indicated by *; all others are GIAO. ^bMAD for 1a isomer A P_B, 8 P_B, and 32 isomer A; scaled chemical shifts for 1a isomer A P_A (which has a P–C single bond) are shown for comparison but are not included in the MAD calculation, and scaled chemical shifts for 8 P_A are not included because these are correctly calculated by all methods previously (Table 2).