500 Inorganic Chemistry, Vol. 40, No. 3, 2001
Thorman et al.
MHz, 20 °C) or Bruker DRX (400 MHz, 25 °C) spectrometer. Chemical
shifts were referenced to proton solvent impurities (δ 7.15 ppm, C6D5H).
UV-vis data were recorded on a HP8452A diode array spectropho-
tometer and reported as λmax in nm (log ꢀ). Elemental analyses were
performed by Iowa State University Instrument Services. Although
hotter, longer combustion conditions were used, carbon analysis was
often low. For metalloporphyrin complexes, this is likely due to the
formation of metal carbides during combustion.9
and C6D6 (≈0.6 mL). Within 5 min all the 3-hexyne had been displaced
and a small amount of (TTP)TidO was present. Allowing the solution
1
to stand at 25 °C for 96 h produced (TTP)TidO in 43% yield. H
NMR (C6D6, 300 MHz): (TTP)TidO,11 9.24 (s, 12H, â-pyrrole), 8.00
(d, 8H, meso-C6H4CH3), 7.28 (d, 8H, meso-C6H4CH3), 2.42 (s, 12H,
meso-C6H4CH3).
Reaction of 1 with tBuNCSe. An NMR tube equipped with a Teflon
stopcock was charged with 1 (12.27 mg, 15.36 µmol), Ph3CH (95.0
(TTP)TidNiPr, 2. Method A: Isopropylisocyanate (44 µL, 0.448
mmol) was added to a stirred solution of 1 (304 mg, 0.380 mmol) in
toluene (≈10 mL). After 1 h at ambient temperature the dark blue
solution was filtered and the filtrate reduced to dryness in vacuo.
Recrystallization at -25 °C for 1 day from a toluene solution (8 mL)
layered with heptane (4 mL) afforded analytically pure product (128
mg, 44% yield). UV/vis (toluene): 549 (4.53), 424 (5.57), 399
(shoulder, 4.70). 1H NMR (C6D6, 400 MHz): 9.24 (s, 12H, â-pyrrole),
8.27 (d, 4H, meso-C6H4CH3), 8.05 (d, 4H, meso-C6H4CH3), 7.31 (t,
8H, meso-C6H4CH3), 2.42 (s, 12H, meso-C6H4CH3), -0.45 (m, 1H,
-NCHMe2), -1.66 (d, 6H, -NCHMe2). Anal. Calcd. for C51H43N5Ti:
C, 79.16; H, 5.60; N, 9.05. Found: C, 78.72; H, 5.67; N, 8.73. Method
B: An NMR tube equipped with a Teflon stopcock was charged with
complex 1 (14.3 mg, 17.8 µmol), Ph3CH (89.5 µL of 0.1455 M in
C6D6, 13.0 µmol), iPrNdCdNiPr (3.2 µL, 20.4 µmol), and C6D6 (≈0.6
mL). The solution immediately darkened and the imido complex (TTP)-
TidNiPr (14.2 µmol, 79% yield) had formed over 12 h at ambient
µL, 0.146 M, 13.82 µmol), BuNCSe (5.4 mg, 33.3 µmol), and C6D6
t
(≈0.6 mL). The solution was allowed to stand at 25 °C for 4 h at which
t
time BuNC (14.73 µmol) and (TTP)TidSe (15.20 µmol, 99% yield)
were observed. Further monitoring of the sample revealed that after
all the (TTP)TidSe was formed, (TTP)Ti(η2-Se2) was being produced
t
1
by the reaction between (TTP)TidSe and excess BuNCSe. H NMR
(C6D6, 300 MHz): (TTP)TidSe,4a 9.31 (s, 8H, â-H), 8.18 (d, 4H, meso-
C6H4CH3), 7.95 (d, 4H, meso-C6H4CH3), 7.28 (m, 8H, meso-C6H4CH3),
t
2.41 (s, 12H, meso-C6H4CH3); BuNC, 0.86 (s, 9H); (TTP)Ti(η2-Se2),
9.08 (s, 8H, â-H), 8.15 (d, 4H, meso-C6H4CH3), 7.89 (d, 4H, meso-
C6H4CH3), 7.26 (m, 8H, meso-C6H4CH3), 2.39 (s, 12H, meso-C6H4CH3).
At early times an intermediate was observed. 1H NMR (C6D6, 300 MHz)
[(TTP)Ti(η2-tBuNCSe)]: 9.01 (s, 8H, â-H), 8.43 (d, 4H, meso-C6H4-
CH3), 7.96 (d, 4H, meso-C6H4CH3), 7.29 (dd, 8H, meso-C6H4CH3), 2.39
(s, 12H, meso-C6H4CH3), -0.52 (s, 9H, η2-tBuNCSe).
Reaction of 1 with Cy3PdS. An NMR tube equipped with a Teflon
stopcock was charged with 1 (8.9 mg, 11.12 µmol), Ph3CH (92.5 µL,
0.146 M, 13.46 µmol), Cy3PdS (4.0 mg, 12.8 µmol), and C6D6 (≈0.6
mL). After ≈5 min (TTP)TidS (1.47 µmol, 13% yield) and 1 (6.96
1
i
temperature. H NMR (C6D6, 300 MHz): PrNC, 2.84 (spt, 1H), 0.65
(d, 6H). The 1H NMR spectrum of (TTP)TidNiPr was experimentally
identical to that reported in Method A.
1
µmol) were present. H NMR (C6D6, 300 MHz): (TTP)TidS,4a 9.29
i
Reaction of Complex 1 with PrNCO. An NMR tube equipped
(s, 12H, â-pyrrole), 8.14 (d, 4H, meso-C6H4CH3), 7.95 (d, 4H, meso-
C6H4CH3), 7.30 (m, 8H, meso-C6H4CH3), 2.41 (s, 12H, meso-C6H4CH3).
(TTP)Ti(PEt3)2, 6. A stirred solution of complex 1 (230 mg, 0.287
mmol) in toluene (≈10 mL) was treated with PEt3 (120 µL, 0.812
mmol). After being stirred for 1.5 h at ambient temperature, the solution
was filtered and the filtrate reduced to dryness in vacuo. The residue
was recystallized from a toluene/hexanes (2:1) solution that was allowed
to stand at -25 °C for 1 day, which produced analytically pure black
crystals of complex 6 in two crops (145 mg, 53% yield). UV/vis
(toluene): 553(4.45), 426 (5.53), 406 (shoulder, 2.61). 1H NMR (C6D6,
400 MHz): 11.50 (bd, 12H, J ) 7 Hz, P(CH2CH3)3, 7.22 (bs, 18H,
P(CH2CH3)3), 6.14 (d, 8H, J ) 8 Hz, meso-C6H4CH3), 4.82 (d, 8H, J
) 8 Hz, meso-C6H4CH3), 1.47 (s, 12H, meso-C6H4CH3), -5.92 (bs,
8H, â-pyrrole). Anal. Calcd. for C60H66N4P2Ti: C, 75.62; H, 6.98; N,
5.88. Found: C, 75.75; H, 7.35; N, 5.80.
(TTP)Ti[(OP(Oct)3)]2, 7. A round-bottom flask was charged with
complex 1 (364 mg, 0.455 mmol) and OdP(Oct)3 (362 mg, 0.935
mmol). Upon addition of toluene (≈15 mL), the stirred solution became
dark blue. The solution was concentrated in vacuo after 2.5 h to a black
oil (≈1 mL). This oil was redissolved in hexanes (≈24 mL) and then
reduced in vacuo to 4 mL and cooled to -25 °C for 1 day, which
produced analytically pure black crystals of complex 7 (355 mg, 52%
yield). UV/vis (hexane): 550 (2.14), 422 (5.69), 403 (shoulder, 2.98).
1H NMR (C6D6, 300 MHz): 12.11 (bs, 12H, 2-CH2), 10.27 (bs, 12H,
3-CH2), 8.72 (d, 8H, meso-C6H4CH3), 4.65 (bs, 12H, 4-CH2), 4.55 (s,
12H, meso-C6H4CH3), 3.03 (bs, 12H, 5-CH2), 2.02 (bs, 12H, 6-CH2),
1.33 (bs, 12H, 7-CH2), 1.18 (bs, 18H, 8-CH3), -0.43 (d, 8H, meso-
C6H4CH3), -33.0 (bs, 8H, â-pyrrole). 31P NMR (C6D6, 81 MHz): 83.5
ppm, referenced to internal H3PO4 (0.00 ppm). (Free OdP(Oct)3, -31.8
ppm) Anal. Calcd. for C96H138N4O2P2Ti: C, 77.39; H, 9.34; N, 3.76.
Found: C, 76.89; H, 9.06; N, 3.08.
with a Teflon stopcock was charged with complex 1 (13.1 mg, 16.4
µmol), Ph3CH (92.0 µL, 0.146 M, 13.4 µmol), iPrNCO (2.60 µL, 26.5
µmol), and C6D6 (≈0.6 mL). Within 5 min (TTP)TidNiPr (16.6 µmol,
1
100% yield) was produced. The H NMR spectrum of (TTP)TidNiPr
was experimentally identical to that reported in Method A.
t
Reaction of Complex 1 with BuNCO. An NMR tube equipped
with a Teflon stopcock was charged with complex 1 (5.93 mg, 7.43
µmol), Ph3CH (84.0 µL, 0.181 M, 15.2 µmol), tBuNCO (1.2 µL, 10.5
µmol), and C6D6 (≈0.6 mL). Within 5 min (TTP)TidNtBu was
produced in 48% yield. Allowing the solution to stand at 25 °C for 16
h produced (TTP)TidNtBu (7.39 µmol, 99% yield) as the only
1
observable diamagnetic porphyrin species. The H NMR is identical
to the literature spectrum for (TTP)TidNtBu:10 9.24 (s, 12H, â-pyrrole),
8.32 (d, 4H, meso-C6H4CH3), 8.04 (d, 4H, meso-C6H4CH3), 7.34 (d,
4H, meso-C6H4CH3), 7.30 (d, 4H, meso-C6H4CH3), 2.42 (s, 12H, meso-
C6H4CH3), -1.58 (s, 9H, -NtBu). CO was detected in a separate
experiment with a Kratos MS50TC mass spectrometer. Calcd.: 27.99491
m/z. Found: 27.99491 ( 0.0028 m/z.
Reaction of 1 with tBuNCS. An NMR tube equipped with a Teflon
stopcock was charged with 1 (10.65 mg, 13.33 µmol), Ph3CH (92.5
µL, 0.1455 M, 13.46 µmol), tBuNCS (2.8 µL, 22.07 µmol), and C6D6
(≈0.6 mL). When the solution was allowed to stand at 25 °C for 13 h,
1
(TTP)TidS (12.94 µmol, 97% yield) was produced. H NMR (C6D6,
300 MHz): CNtBu, 0.86 (s, 9H); (TTP)TidS,4a 9.29 (s, 12H, â-pyrrole),
8.14 (d, 4H, meso-C6H4CH3), 7.95 (d, 4H, meso-C6H4CH3), 7.30 (m,
8H, meso-C6H4CH3), 2.41 (s, 12H, meso-C6H4CH3).
Reaction of Complex 1 with CS2. An NMR tube equipped with a
Teflon stopcock was charged with complex 1 (12.2 mg, 15.3 µmol),
Ph3CH (85.0 µL, 0.181 M, 15.4 µmol), CS2 (1.2 µL, 20.0 µmol), and
C6D6 (≈0.6 mL). Heating the solution at 80 °C for 112 h produced
(TTP)TidS (12.5 µmol, 82% yield). 1H NMR (C6D6, 300 MHz) (TTP)-
TidS:4a 9.29 (s, 8H, â-H), 8.14 (d, 4H, meso-C6H4CH3), 7.95 (d, 4H,
meso-C6H4CH3), 7.30 (m, 8H, meso-C6H4CH3), 2.41 (s, 12H, meso-
C6H4CH3).
Structure Determination of (TTP)Ti(PEt3)2, 6 and (TTP)Ti[OP-
(Oct)3]2, 7. Crystallographic data for complexes 6 and 7 are found in
Table 1. A crystal of complex 7 was attached to a glass fiber and
mounted on a Siemens SMART system for data collection at 173(2)
K. Final cell constants were calculated from a set of 8192 strong
reflections from the actual data collection. The space group P21/n was
Reaction of Complex 1 with (MeO)2SO. An NMR tube equipped
with a Teflon stopcock was charged with complex 1 (6.3 mg, 7.7 µmol),
Ph3CH (90.5 µL, 0.145 M, 13.1 µmol), (MeO)2SO (1.7 µL, 20.0 µmol),
determined from systematic absences and intensity statistics.12
A
(9) Ikeda, O.; Fukuda, H.; Tamura, H. J. Chem. Soc., Faraday Trans. 1
1986, 82, 1561-1573.
(10) Gray, S. D.; Thorman, J. L.; Berreau, L. M.; Woo, L. K. Inorg. Chem.
1997, 36, 278.
(11) Fournari, C.; Guilard, R.; Fontesse, M.; Latour, J.-M.; Marchon, J.-
C. J. Organomet. Chem. 1976, 110, 205.
(12) SHELXTL-Plus V5.0; Siemens Industrial Automation, Inc.: Madison,
WI, 1998.