Table 3.

Experimental^a and scaled^{b 31}P NMR chemical shifts^c for the compounds shown in Figure 5, Figure 6, and Figure 7.

Optimization functional:		B3LYP	M06-2X	M06-2X	PBE0
NMR functional:		B3LYP	B3LYP	M06-2X	PBE0d
Compound	Exp.e
11 f	152.9 [75]	156.9	153.3	152.1	166.5
12 f	139.3 [75]	142.0	138.5	139.3	150.6
13	133.0 [76]	133.8	125.4	125.0	128.8
14 f	136.7 [76]	144.8	128.8	132.0	138.8
15 f	132.2[74]	129.3	126.4	124.7	137.5
16 f	138.5 [74]	142.1	137.2	134.8	150.3
17 f	125.8 [74]	128.6	126.2	124.9	133.7
18 f	145.3 [74]	146.7	144.5	142.3	152.8
19 g	169 [77]	181.3	178.9	172.3	186.0
20 g	153 [77]	147.8	146.4	148.7	169.2
21 h	355.7 [78]	350.9	355.2	398.1	372.4
21 (Ph3P)	26.2	20.7	19.2	23.8	20.9
22 i	302 [79]	310.4	299.7	350.9	306.4j
23	−127.2 [80]	−125.7	−124.8	−107.0	−130.0
24	−151.0 [80]	−129.0	−131.2	−120.6	−140.3
25	63.5 [81]	64.7	68.7	73.6	63.6
26	187.9 [71]	181.7	182.1	224.9	197.3
27 f	13.9 [82]	11.0	12.3	17.7	19.6
28	16.0 [82]	14.2	15.4	20.6	22.7
29 g	93 [77]	80.8	97.1	104.6	94.1
anti-30	24.2 [83]	34.8	25.2	17.9	18.8
syn-30f	11.3 [83]	23.5	15.6	9.1	7.8
anti-30[O]	54.1 [83]	44.8	42.1	45.4	44.7
syn-30[O]f	61.8 [83]	49.7	46.3	49.3	50.1
anti-31	−24.4	−12.1	−29.2	−27.9	−31.2
syn-31	−21.8	−0.9	−21.4	−19.6	−22.2
32 f	−181	−59.2	−169.3	−180.1	−119.8
33	−79	−78.8	−74.7	−72.1	−90.3
34	−14	−3.6	−11.2	−10.0	−20.4
33[O]	38	27.2	30.3	36.3	24.6
34[O]	26	12.6	13.7	20.8	11.0
11–34[O]
MAD/RMSDk		11.1/23.7	5.4/7.3	9.7/15.8	9.8/14.4
1a–34[O]
MAD/RMSD		11.9/21.8	7.1/9.9	10.3/16.3	8.2/12.3
2–7, 9–20, 27–34[O]l
MAD/RMSD		12.0/22.8	6.4/8.5	5.4/7.1	8.7/13.1

^a,b,c,dSee notes a–d for Table 2; NMR basis sets and solvation were 6-311+G(2d,p) and CHCl₃ except for PBE0 (6-311G(2d,2p) and gas phase). ^eCompounds 11, 12, and 30–31 were optimized and the NMR spectra calculated in toluene, 13, 14, 19, 20, 25, 26, 29, and 32–34[O] in chloroform, 15–18, 23, 24, 27, and 28 in benzene, 21 in dichloromethane, and 22 in acetonitrile. ^fMajor conformations shown in Figures 5–7 but compounds 11, 12, 14, 16–18, 27, syn-30, syn-30[O], and 32 exhibit multiple conformations; for 16 twist-boat 1 and twist-boat 2 are significant, and for 17 the chair and twist boat 1 are significant; for 15 only the chair was significant (Table S7, Supporting Information File 1). ^gOptimizations and NMR calculations were carried out on the compounds without the methyl groups para to the oxygen atoms due to problems with convergence because of methyl rotation; no significant chemical shift differences were seen. ^hBF₄¯ rather than the actual AlCl₄¯ ions were used in the calculations to minimize the size of the calculation. ⁱPF₆¯ and Cl¯ ions rather than the actual SbF₆¯ and Br¯ ions were used in the calculations to minimize the size of the calculation. ^jIn the absence of solvation the trication structure could not be optimized in the presence of anions so this calculation is for the trication alone. ^kSee note a in Table 1. ^lCombined MAD/RMSD for all compounds in Table 2 and Table 3 with no multiple P–C bonds.