C–P), 128.41 (d, 2JC–P = 12.5 Hz, o-Ph), 122.74 (d, 2JC–P = 7.9 Hz,
pyrrole C2), 109.18 (d, 3JC–P = 7.7 Hz, pyrrole C3), 107.65 (pyrrole
TiCl(NMe2){NC4H3CH2POPh2}2 (6a). On dissolving 5a
(0.07 g, 0.10 mmol) in dichloromethane in an NMR tube an
orange solution was obtained. Over a period of 2 h the solution
turned dark red. After removal of all volatiles under vacuo the
title complex was observed as a dark-red solid (0.07 g, 0.10 mmol,
100%). Anal Calc for TiC36H36ClN3O2P2: C, 62.85; H, 5.27; N,
1
C5), 47.52 (NMe2), 30.39 (d, JC–P= 64.8 Hz, CH2P) ppm. 31P{ H}
NMR (121 MHz, 300 K, C6D6,): d 40.05 ppm.
Ti(NMe2)3{NC4H3(4-But)CH2P(O)Ph2} (4c). This com-
pound was synthesised as described for complex 4a and
obtained as a yellow-orange solid in 65% yield. Anal Calc for
TiC27H41N4OP: C, 62.79; H, 8.00; N, 10.85. Found: C, 62.80; H,
1
6.11, Found; C, 62.43; H, 5.15; N, 6.26 H NMR (300 MHz,
300 K, CD2Cl2): d 7.59–7.31 (m, 20H, Ph), 7.10 (s, 1H, pyrrole),
7.05–7.00 (m, 1H, pyrrole), 6.60–6.55 (s, 1H, pyrrole), 5.99–5.97 (s,
2H, pyrrole), 5.59 (s, 1H, pyrrole), 4.70 (ddd, 1H, 2JH-P = 16.6 Hz,
2J = 7.4 Hz, 4J = 3.9 Hz, PCHH), 4.22 (ddd, 1H, 2JH-P = 16.0 Hz,
1
7.89; N, 10.51. H NMR (300 MHz, 300 K, C6D6): d 7.32–7.26
(m, 4H, Ph), 7.12–7.08 (m, 7H, Ph + pyrrole H5), 6.11 (s, 1H,
pyrrole H3), 3.59 (d, 2H, 2JH-P = 12.00 Hz, PCH2), 3.53, (s, 18H,
2J = 6.3 Hz, 4J = 4.1 Hz, PCHH), 3.88 (dd, 1H, 2JH-P = 9.2 Hz,
1
NMe2), 1.68 (s, 9H, But) ppm. 31P{ H}-NMR (121 MHz, 300 K,
2
2J = 6.3 Hz, PCHH), 3.77 (s, 6H, NMe2) 3.43 (dd, 1H, JH-P
=
C6D6,): d 40.22 ppm.
7.4 Hz, J = 7.4 Hz, PCHH) ppm. 31P{ H} NMR (121 MHz,
2
1
Ti(NMe2)2{NC4H3CH2P(O)Ph2}2 (5a). To a suspension of 3a
(0.2 g, 0.7 mmol) in toluene (40 cm3) at -78 ◦C was slowly added
Ti(NMe2)4 (0.08 cm3, 0.35 mmol) in toluene (25 cm3), resulting
in an orange solution. The solvent and excess Ti(NMe2)4 were
removed under reduced pressure and the orange solid residue was
washed with light petroleum (100 cm3) and ext◦racted in toluene (3 ¥
75 cm3). Cooling of the toluene solution to 5 C overnight yielded
orange crystals of 5a (0.41 g, 85%). Anal Calc for TiC38H42N4O2P2:
C, 65.52; H, 6.08; N, 8.04%. Found: C, 65.10; H, 6.16; N 7.95%.
1H NMR (300 MHz, 300 K, CD2Cl2): d 7.70–7.32 (m, 20H, Ph),
6.87 (br s, 2H, pyrrole), 6.33 (br s, 2H, pyrrole), 5.94 (br s, 2H,
pyrrole), 4.12 (br m, 1H, PCHH), 3.59 (s, 12H, NMe2), 3.22 (br
300 K, CD2Cl2): 44.65, 44.33 ppm.
TiCl(NMe2){NC4H3(4-But)CH2P(O)Ph2)2 (6c). On dissolving
5c (0.08 g, 0.10 mmol) in CD2Cl2 in an NMR tube an orange
solution was obtained which darkened to red over 2 h at
20 ◦C. After removal of all volatiles under vacuum, 6c was
observed as a dark-red solid as a mixture of two isomers (70:30)
(0.08 g, 0.10 mmol, 100%). Anal Calc for TiC36H36ClN3O2P2: C,
66.04; H, 6.55; N, 5.25, Found; C, 65.56; H, 6.38; N, 5.31. The same
products was produced by reaction of 5c with 1.4 equivalents of
1
trimethylchlorosilane in hexanes. H NMR (300 MHz, 300 K,
CD2Cl2) (most abundant isomer only): d 7.95–6.92 (m, 20H, Ph),
6.98–6.92 (m, 1H, pyrrole H5), 6.44–6.37 (s, 1H, pyrrole H5), 5.81
(s, 1H, pyrrole H3), 5.41 (s, 1H, pyrrole H3), 4.86–4.75 (m, 1H,
1
m, 1H, PCHH) ppm. 31P{ H} NMR (121 MHz, 300 K, C6D6): d
40.49 ppm.
PCHH), 4.29–4.18 (m, 1H, PCHH), 3.69 (br s, 7H, NMe2
+
Ti(NMe2)2{NC4H3(4-But)CH2P(O)Ph2}2 (5c). The com-
pound was made as described for 5a in 78% yield as orange
crystals suitable for X-ray crystallography. Anal Calc for
TiC46H58N4O2P2: C, 68.31; H, 7.23; N, 6.93%. Found: C, 68.83;
PCHH), 3.34 (dd, 1H, 2JH-P = 8.7, 2J = 5.3Hz, PCHH), 1.26 (s, 9H,
But), 1.19 (s, 9H, But) ppm. 13C NMR (75 MHz, 300 K, CD2Cl2)
(most abundant isomer only): d 132.84–127.63 (m, pyrrole C4 +
Ph), 127.23 (d, 5JC–P = 1.6 Hz pyrrole C5), 125.69 (d, 5JC–P = 1.3 Hz
1
H, 7.81; N, 7.12%. H NMR (300 MHz, 300 K, CD2Cl2): d 7.76
pyrrole C5), 123.90 (d, 2JC–P = 7.3 Hz pyrrole C2), 123.73 (d, 2JC–P
=
(br s, 2H, pyrrole H5), 7.24–6.80 (m, 20H, Ph), 6.08 (br s, 2H,
3
7.3 Hz pyrrole C2), 105.30 (d, JC–P = 7.7 Hz pyrrole C3), 104.21
(d, 3JC–P = 8.2 Hz pyrrole C3), 51.61 (NMe2), 32.37 (CMe3), 31.90
(CMe3), 31.81 (CMe3), 31.12 (d, JC–P = 84.3 Hz, CH2P), 30.36
pyrrole H3), 4.08–3.96 (m, 1H, PCHH), 3.74 (s, 12H, NMe2), 3.22
2
2
(dd, JH–P = 8.9 Hz, JH–H = 5.1 Hz, 1H, PCHH), 1.74 (s, 9H,
But) ppm. 13C NMR (75 MHz, 300 K, C6D6): 132.51 (pyrrole C4),
1
(CMe3) ppm. 31P{ H} NMR (121 MHz, 300 K, CD2Cl2): 50.25,
2
132.16–131.41 (m. Ph), 125.79 (pyrrole C5), 121.49 (d, JC–P
=
48.04 (minor isomer) 43.96, 43.00 (major isomer).
9.2 Hz, pyrrole C2), 106.44 (d, JC–P = 6.5 Hz, pyrrole C3),
3
50.30 (NMe2), 33.00 (CMe3), 31.61 (d, JC–P = 65.8 Hz, CH2P),
Zn{NC4H3(5-But)CH2P(O)Ph2}2 (7b). To a solution of 3b
(0.88 g, 2.6 mmol) in toluene (40 cm3) was added Zn[N(SiMe3)2]2
(0.5 g, 1.3 mmol). The resultant orange solution was left to stir
overnight. After removal of volatiles in vacuo the product was
washed with light petroleum, extracted into toluene, filtered and
cooled to -30 ◦C for 24 h to give 7b as colourless blocks (0.49 g,
77%). Anal. Calcd. for C42H46N2O2P2Zn: C, 68.34; H, 6.28; N,
31.05 (CMe3) ppm. 31P{ H} NMR (121 MHz, 300 K, C6D6): d
1
40.32 ppm.
Ti(NMe2)2{NC4H3CH2P(O)Cy2}2 (5d). The compound was
prepared from 3d as described for 5a in 61% yield as orange crystals
suitable for X-ray crystallography. Anal Calc for TiC38H66N4O2P2:
C, 63.32; H, 9.23; N, 7.77; Found; C, 62.93; H, 8.91; N, 7.32. 1H
NMR (300 MHz, 300 K, C6D6): d 8.12 (m, 1H, pyrrole H4), 7.05
(s, 1H, pyrrole H4), 6.90 (m, 1H, pyrrole H5), 6.61 (m, 1H, pyrrole
H5), 6.41 (m, 1H, pyrrole H3), 6.35 (s, 1H, pyrrole H3), 3.84–2.89
(m, 2H, PCHH), 3.63 (s, 6H, NMe2), 3.61 (s, 6H, NMe2), 3.32–
3.23 (m, 1H, PCHH), 3.06–2.97 (m, 1H, PCHH), 1.86–1.03 (m,
44H, Cy) ppm. 13C NMR (75 MHz, 300 K, C6D6): d 131.94 (d,
1
3.80%. Found: C, 68.2; H, 6.34; N, 3.75%. H NMR (300 MHz,
300 K, C6D6): d 7.63–7.53 (m, 8H, Ph), 7.24–6.99 (m, 12H, Ph),
6.64 (d, 2H, 3J = 3.02, pyrrole H3), 6.46–6.45 (m, 2H, pyrrole H4),
4.15 (dd, 2H, 2JC–P = 12.3 Hz, 2J = 3.6 Hz, CHHP) 3.95 (dd, 2H,
2JC–P = 12.1 Hz, 2J = 4.0 Hz, CHHP), 1.79 (s, 18H, But) ppm. 13
C
NMR (75 MHz, 300 K, C6D6): d 151.58 (d, 5JC–P = 2.5 Hz, pyrrole
C5), 132.83 (d, 4JC–P = 2.4 Hz, p-Ph), 132.08 (d, 4JC–P = 2.4 Hz, p-
Ph), 131.71 (d, 3JC–P = 10.3 Hz, m-Ph), 131.45 (d, 3JC–P = 10.3 Hz,
4
4JC-P = 1.0 Hz, pyrrole C4), 131.46 (d, JC-P = 1.0, pyrrole C4),
124.55 (d, 2JC–P = 9.2 Hz, pyrrole C2), 123.19 (d, 2JC–P = 10.2 Hz,
pyrrole C2), 106.69–106.00 (m, pyrrole C3 + C5), 51.58 (NMe2),
m-Ph), 130.42 (d, JC–P = 60.6 Hz, aromatic C–P), 129.29 (d, JC–P =
48.76 (NMe2), 35.37 (d, JC–P = 56.5 Hz, CH2P), 34.59 (d, JC–P
=
54.5 Hz, aromatic C–P), 128.52 (d, 2JC–P = 12.1 Hz, o-Ph), 124.12
(d, 2JC–P = 11.3 Hz, pyrrole C2), 109.94 (d, 3JC–P = 8.0 Hz, pyrrole
C3), 104.32 (pyrrole C4), 32.93 (CMe3), 32.65 (d, JC–P = 86.0 Hz,
1
64.09 Hz, CH2P), 27.07–25.08 (m, 24C, Cy) ppm. 31P{ H}-NMR
(121 MHz, 300 K, C6D6): d 62.29, 58.54 ppm.
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8269–8279 | 8277
©