1
[
Ti
4
(
3
-O)(OiPr)
5
(-OiPr)
3
(O
3
PPhOMe)
3
]·iPrOH (3): 59% yield. H NMR (500 MHz, CDCl
3
) ,
),
), 1.43 (d, JH–H = 6.0 Hz, 18H, bridged
3
ppm: 1.10 (d, JH–H = 6.0 Hz, 24H, crystal solvent and coordinated iPrOH, and terminal OCH(CH
3
)
2
3
3
1
.33 (d, JH–H = 6.0 Hz, 18H, terminal OCH(CH
3
)
2
OCH(CH
3
)
2
), 3.67 (s, 2H, OH), 3.77 (s, 9H, OCH
3
), 4.47 (br s, 4H, solvent and terminal
3
3
OCH(CH
3
)
2
), 4.66 (sept, JH–H = 6.0 Hz, 3H, terminal OCH(CH
3
)
2
), 5.00 (sept, JH–H = 6.0 Hz, 3H,
3
4
3
bridged OCH(CH
3
)
2
), 6.84 (dd, JH–H = 8.5 Hz, JP–H = 2.5 Hz, 6H, Ar), 7.81 (dd, JH–H = 8.5 Hz,
3
13
1
J
P–H = 13.5 Hz, 6H, Ar). C{ H} NMR (126 MHz, CDCl
3
) , ppm: 24.55, 24.82, 24.86, 54.92,
2
1
3
7
1
8.24, 79.18, 112.71 (d, JP–C = 16.4 Hz, Ar), 126.22 (d, JP–C = 210.5 Hz, Ar), 132.91 (d, JP–C
=
4
31
1
0.6 Hz, Ar), 160.74 (d, JP–C = 3.8 Hz, Ar). P{ H} NMR (202 MHz, CDCl
3
) , ppm: 8.6, 9.6.
–
1
FT-IR (ATR/cm ): 3482, 2970, 2931, 2863, 2838, 1601, 1573, 1505, 1463, 1442, 1375, 1362, 1326,
1
6
320, 1293, 1253, 1197, 1158, 1135, 1105, 1092, 1081, 1034, 993, 977, 944, 850, 826, 812, 801, 683,
61, 613, 591, 553. Ceramic yield: 39.4% (calcd. for Ti
4
P
3
O
16, 39.8%).
1
[
Ti
4
(
3
-O)(OiPr)
5
(-OiPr)
3
(O
3
PPhF)
3
]·iPrOH (4): 12% yield. H NMR (500 MHz, CDCl
3
) ,
3
3
ppm: 1.09 (d, JH–H = 6.0 Hz, 24H, solvent, coordinated and terminal OCH(CH
3
)
2
), 1.33 (d, JH–H
=
3
6
2
3
.5 Hz, 18H, terminal OCH(CH
3
)
2
), 1.42 (d, JH–H = 6.0 Hz, 18H, bridged OCH(CH
3
3
)
2
), 3.43 (br s,
H, OH), 4.42 (br s, 4H, solvent, coordinated and terminal OCH(CH
3
)
2
), 4.66 (sept, JH–H = 6.5 Hz,
3
H, terminal OCH(CH
3
)
2
), 5.01 (sept, JH–H = 6.0 Hz, 3H, bridged OCH(CH
3
)
2
), 7.01 (ddd (like-td),
13
1
J = 3.5 Hz, 9.5 Hz, 6H, Ar), 7.86 (ddd, J = 6.0 Hz, 8.0 Hz, 13.0 Hz, 6H, Ar). C{ H} NMR (126
MHz, CDCl ) , ppm: 24.59, 24.79, 24.87, 78.54, 78.77, 79.59, 79.76, 114.48 (dd, J = 16.4, 82.2 Hz,
Ar), 130.32 (dd, J = 3.8, 207.6 Hz, Ar), 133.51 (dd, J = 8.6, 10.6 Hz, Ar), 163.99 (dd, J = 3.9, 249.0
3
31
1
19
1
Hz, Ar). P{ H} NMR (202 MHz, CDCl
3
) , ppm: 7.0, 8.3. F{ H} NMR (471 MHz, CDCl
3
) ,
ppm: −109.96, −110.16. FT-IR (ATR/cm ): 3068, 2971, 2930, 2865, 1595, 1499, 1464, 1377, 1362,
327, 1224, 1195, 1159, 1131, 1110, 1088, 1042, 998, 977, 950, 881, 853, 831, 683, 605. Ceramic
yield: 41.7% (calcd. for Ti 16, 42.8%).
–
1
1
4 3
P O
1
[
Ti
4
(
3
-O)(OiPr)
5
(-OiPr)
3
(O
3
PPhCl)
3
]·iPrOH (5): 13% yield. H NMR (500 MHz, CDCl
3
) ,
3
3
ppm: 1.08 (d, JH–H = 5.5 Hz, 24H, solvent, coordinated and terminal OCH(CH
3
)
2
), 1.33 (d, JH–H
=
3
6
2
.0 Hz, 18H, terminal OCH(CH
3
)
2
), 1.41 (d, JH–H = 6.0 Hz, 18H, bridged OCH(CH
3
)
2
), 3.68 (br s,
3
H, OH), 4.39 (br s, 4H, solvent and terminal OCH(CH
)
3 2
), 4.65 (sept, JH–H = 6.0 Hz, 3H, terminal
3
4
3
OCH(CH
3
)
2
), 5.00 (sept, JH–H = 6.0 Hz, 3H, bridged OCH(CH
3
)
2
), 7.31 (dd, JP–H = 3.0 Hz, JH–H
=
3
3
13
1
8
.5 Hz, 6H, Ar), 7.80 (dd, JH–H = 8.5 Hz, JP–H = 13.0 Hz, 6H, Ar). C{ H} NMR (126 MHz,
2
CDCl
3
) , ppm: 24.56, 24.72, 24.78, 24.86, 78.68, 79.63, 79.74, 127.64 (d, JC–P = 15.4 Hz, Ar),
3
1
4
1
32.63 (d, JC–P = 10.6 Hz, Ar), 133.29 (d, JC–P = 205.8 Hz, Ar), 135.88 (d, JC–P = 4.8 Hz, Ar).
31
1
–1
P{ H} NMR (202 MHz, CDCl
3
) , ppm: 6.6, 7.7. FT-IR (ATR/cm ): 3481, 3065, 2974, 2932,
2
8
862, 1584, 1563, 1481, 1463, 1449, 1377, 1362, 1327, 1202, 1135, 1114, 1086, 1060, 988, 948, 852,
4 3
35, 821, 753, 596, 560. Ceramic yield: 38.4% (calcd. for Ti P O16, 39.4 %).
1
Ti
7
(
3
-O)
2
(OiPr)
6
(-OiPr)
6
(O
3
PBnBr)
6
(6): 40% yield. H NMR (500 MHz, CDCl
3
) , ppm: 1.36
),
), 4.94 (sept,
3
3
(
d, JH–H = 6.0 Hz, 36H, terminal OCH(CH
3
)
2
), 1.38 (d, JH–H = 6.5 Hz, 36H, bridged OCH(CH
3
)
2
2
3
2.57 (d, JP–H = 23.5 Hz, 12H, CH
2
), 4.69 (sept, JH–H = 6.0 Hz, 6H, terminal OCH(CH
3
)
2