Synthesis and reactivity of hydrazido(2-) and imido derivatives of titanium(IV) tetratolylporphyrin

Article abstract of DOI:10.1021/ic990991l

Titanium porphyrin hydrazido complexes (TTP)Ti = NNR₂ (TTP = meso-tetra-p-tolylporphyrinato dianion; R = Me (1), Ph (2)) were synthesized by treatment of (TTP)TiCl₂ with 1,1-disubstituted hydrazines H₂NNR₂ (R =

Full text of DOI:10.1021/ic990991l

Inorg. Chem. 2000, 39, 1301-1304
1301
Synthesis and Reactivity of Hydrazido(2-) and Imido Derivatives of Titanium(IV)
Tetratolylporphyrin
Joseph L. Thorman and L. Keith Woo*
Department of Chemistry, Iowa State University, Ames, Iowa 50011-3111
ReceiVed August 17, 1999
Titanium porphyrin hydrazido complexes (TTP)TidNNR2 (TTP ) meso-tetra-p-tolylporphyrinato dianion; R )
Me (1), Ph (2)) were synthesized by treatment of (TTP)TiCl2 with 1,1-disubstituted hydrazines H2NNR2 (R )
Me, Ph) in the presence of piperidine. The nucleophilic character of the hydrazido moiety was demonstrated in
the reactions of complexes 1 and 2 with p-chlorobenzaldehyde, which yielded the titanium oxo complex (TTP)-
TidO and the respective hydrazones. Protonation of complexes 1 and 2 with phenol or water produced the 1,1-
disubstituted hydrazine along with (TTP)Ti(OPh)2 or (TTP)TidO, respectively. Similar reactivity of p-chlorobenz-
aldehyde and phenol with (TTP)TidNiPr, 3, was observed. The reaction of complex 3 with nitrosobenzene cleanly
i
formed the azo compound PrNdNPh and the terminal oxo product (TTP)TidO.
Introduction
by the decreased steric bulk at the NR. As part of a continuing
study of group 4 metalloporphyrin complexes containing strong
Research dedicated to early transition metal complexes
possessing ligand-metal multiple bonds continues to develop.
A substantial body of investigation concerning group 4 metals
in this area has focused on the relatively electron-rich metal-
locene derivatives.1,2 From these studies, imido complexes have
shown potential as aziridination, hydroamination, and hetero-
cyclization catalysts. In comparison, the reactivity exhibited by
the titanium imido functional group in porphyrin analogues is
less extensive.3 This lower reactivity is presumably due, in part,
to steric factors involving the porphyrin ligand and the imido
substituent.
Although the chemistry of imido complexes is now well
established, investigation of the isolobal hydrazido moiety has
been confined mainly to groups 5-7.4 Examples of group 4
hydrazido(2-) complexes are limited to a dimeric species
[CpClTidNNR2]25 and two monomeric complexes Cp2TidNN-
(TMS)26 and (TMTAA)TidNNPh2.7 Titanium metalloporphyrin
hydrazido(2-) complexes, (TTP)TidNNR2, may offer an ad-
ditional assessment of the reactivity of the TidN moiety, aided
π-donor ligands, we report the synthesis and reactivity of new
examples of titanium hydrazido(2-) complexes.
Experimental Section
General. All manipulations were performed under an atmosphere
of nitrogen using a Vacuum Atmospheres glovebox equipped with a
model MO40-1 Dri-Train gas purifier. All solvents were rigorously
degassed and dried prior to use. Benzene-d6, benzene, toluene, and
hexane were freshly distilled from purple solutions of sodium ben-
zophenone ketyl and brought into the drybox without exposure to air.
Methylene chloride and piperidine were dried by passage through a
column of activated neutral alumina. Literature procedures were used
to prepare (TTP)TidNiPr,8 3, and (TTP)TiCl2.9 The latter compound
was recrystallized from CH2Cl2/hexane prior to use. 1,1-Dimethylhy-
drazine was purchased from Aldrich and dried by passage over a column
of activated neutral alumina. 1,1-Diphenylhydrazonium hydrochloride
was used as received from Aldrich. Nitrosobenzene and p-chloroben-
zaldehyde were purchased from Aldrich and purified by literature
procedures.10 1H NMR data were recorded on either a Varian VXR
(300 MHz, 20 °C) or a Bruker DRX (400 MHz, 25 °C) spectrometer.
Chemical shifts were referenced to proton solvent impurities (δ 7.15,
C6D5H). UV-vis data were recorded on a HP8452A diode array
spectrophotometer and reported as λmax in nm (log ꢀ). Elemental
analyses (C, H, N) were performed by Iowa State University Instrument
Services. MS-CI studies were performed on a Finnigan TSQ 700 at 70
eV in the negative ion mode using ammonia as the ionization gas. GC-
MS studies were performed on a Varian gas chromatograph coupled
to an ITS 40 ion trap mass spectrometer (capillary column DB-5MS).
(1) Leading references concerning terminal chalcogenido complexes. (a)
Trnka, T. M.; Parkin, G. Polyhedron 1997, 16, 1031. (b) Nugent, W.
A.; Mayer, J. M. Metal-Ligand Multiple Bonds; Wiley-Interscience:
New York, 1988.
(2) (a) Housemekerides, C. H.; Ramage, D. L.; Kretz, C. M.; Shontz, J.
T.; Pilato, R. S.; Geoffroy, G. L.; Rheingold, A. L.; Haggerty, B. S.
Inorg. Chem. 1992, 31, 4453. (b) Doxsee, K. M.; Farah, J. B.; Hope,
H. J. Am. Chem. Soc. 1991, 113, 8889.
(3) (a) Gray, S. D.; Thorman, J. L.; Adamian, V.; Kadish, K. M.; Woo,
L. K. Inorg. Chem. 1998, 37, 1. (b) Berreau, L. M.; Young, V. G.,
Jr.; Woo, L. K. Inorg. Chem. 1995, 34, 527.
(TTP)TidNNMe2, 1. To a hexanes (ca. 20 mL) slurry of (TTP)-
TiCl2 (257 mg, 0.326 mmol) was added piperidine (132 µL, 1.33 mmol)
and H2N2Me2 (30 µL, 0.39 mmol). The blue solution was filtered after
being stirred for 12 h at ambient temperature, and the solid was washed
with hexanes (ca. 4 mL). This purple solid was divided into three
approximately equal portions and each placed on a clean fritted filter
(4) (a) Kahlal, S.; Saillard, J. Y.; Hamon, J. R.; Manzur, C.; Carrillo, D.
J. Chem. Soc., Dalton Trans. 1998, 1229. (b) Green, M. L. H.; James,
J. T.; Chernega, A. N. J. Chem. Soc., Dalton Trans. 1997, 1719. (c)
Sutton, D. Chem. ReV. 1993, 93, 995. (d) Henderson, R. A.; Leigh,
G. J.; Pickett, C. J. AdV. Inorg. Radiochem. 1983, 27, 197. (e)
McCleverty, J. A. Transition Met. Chem. 1987, 12, 282.
(5) Hughes, D. L.; Latham, I. A.; Leigh, G. J. J. Chem. Soc., Dalton Trans.
1986, 393.
(8) Thorman, J. L.; Young, V. G., Jr.; Woo, L. K. Manuscript in
preparation.
(6) Wiberg, N.; Haring, H. W.; Huttner, G.; Friedrich, P. Chem. Ber. 1978,
111, 2708.
(7) Blake, A. J.; McInnes, J. M.; Mountford, P.; Nikonov, G. I.; Swallow,
D.; Watkin, D. J. J. Chem. Soc., Dalton Trans. 1999, 379.
(9) Berreau, L. M.; Hays, J. A.; Young, V. G., Jr.; Woo, L. K. Inorg.
Chem. 1994, 33, 105.
(10) Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of
Laboratory Chemicals, 2nd ed.; Pergamon Press: New York, 1980.
10.1021/ic990991l CCC: $19.00 © 2000 American Chemical Society
Published on Web 03/02/2000

1302 Inorganic Chemistry, Vol. 39, No. 6, 2000
Thorman and Woo
and washed with 2 mL of benzene. The combined filtrates were taken
to dryness to yield dark-blue (TTP)TidNNMe2 (118.3 mg, 47% yield)
and a trace of (TTP)TidO. 1H NMR (C6D6, 300 MHz): δ 9.16 (s, 8H,
â-H), 8.20 (d, 4H, JH-H ) 8 Hz, meso-C6H4CH3), 8.04 (d, 4H, JH-H
) 8 Hz, meso-C6H4CH3), 7.31 (t, 8H, 3JH-H ) 8 Hz, meso-C6H4CH3),
2.42 (s, 12H, meso-C6H4CH3), -0.28 (s, 6H, NN(CH3)2). UV/vis
(toluene): 426 (5.65), 548 (4.64) nm. The hydrolytic sensitivity of
complex 1 and resulting contamination with (TTP)TidO precluded
satisfactory elemental analysis.
MHz): δ 9.02 (s, 8H, â-H), 8.01 (d, 8H, 3JH-H ) 7.8 Hz, -C6H4Me),
3
7.26 (d, 8H, JH-H ) 7.8 Hz, -C6H4Me), 5.83 (overlapping d and t,
1
6H, m-, p-C6H5), 2.67 (m, 4H, o-C6H5), 2.38 (s, 12H, CH3). H NMR
3
3
of H2NNMe2 (C6D6, 300 MHz): δ 2.45 (br, 2H, NH), 2.15 (s, 6H,
CH3).
Reaction of (TTP)TidNNPh2 with Phenol. An NMR tube was
charged with complex 2 (6.63 mg, 7.37 µmol), PhOH (16.2 µL, 1.23
M, 19.9 µmol), Ph3CH (92 µL, 0.1743 M) as an internal standard, and
C6D6 (ca. 0.6 mL). Complex 2 was consumed within approximately 5
min to produce (TTP)Ti(OPh)2 (7.11 µmol, 96%) and 1,1-diphenyl-
hydrazine (7.37 µmol, 100%). 1H NMR of H2NNPh2 (C6D6, 300
MHz): δ 7.11 (m, 8H), 6.84 (m, 2H), 3.30 (s, 2H, NH).
(TTP)TidNNPh2, 2. A mixture of H2N2Ph2‚HCl (234 mg, 1.06
mmol), piperidine (173 µL, 1.75 mmol), and 4 Å molecular sieves were
stirred in hexanes (ca. 15 mL) overnight. This mixture was filtered
over a pad of activated neutral alumina and the filtrate added to (TTP)-
TiCl2 (154 mg, 0.196 mmol) and piperidine (ca. 2 mmol). This solution
slowly turned from red-brown to dark-red over 13 h, at which time it
was filtered and the solid washed with hexanes (3 × 6 mL). The dark-
blue solid was placed on a clean fritted filter and washed with 2 mL of
benzene. The benzene was removed in vacuo to afford analytically pure
Reaction of (TTP)TidNiPr with Phenol. An NMR tube was
charged with imido complex 3 (1.4 mg, 1.81 µmol), PhOH (3.6 µL,
1.23 M, 4.43 µmol), Ph3CH (89 µL, 0.1448 M) as an internal standard,
and C6D6 (ca. 0.6 mL). Allowing the solution to stand at ambient
temperature for 21 h produced (TTP)Ti(OPh)2 (1.68 µmol, 93%). The
i
methyl signal of the amine product, NH2 Pr, was obscured by residual
1
hexane.
(TTP)TidNNPh2 (39.7 mg, 23% yield). H NMR (C6D6, 300 MHz):
δ 9.13 (s, 8H, â-H), 8.05 (d, 8H, 3JH-H ) 8 Hz, meso-C6H4CH3), 7.28
(d, 8H, 3JH-H ) 8 Hz, meso-C6H4CH3), 6.31 (m, 6H, m-, p-NN(C6H5)2,
4.34 (d, 4H, 3JH-H ) 8 Hz, o-NN(C6H5)2), 2.41(s, 12H, meso-C6H4CH3).
MS Calcd (found) [M+]: 898.95 (898.3) m/z. Anal. Calcd (found) for
C60H46N6Ti: C, 80.17 (79.97); H, 5.16 (5.24); N, 9.35 (8.49). UV/vis
(toluene): 426 (5.61), 547 (4.69) nm.
Reaction of (TTP)TidNNMe2 with Water. An NMR tube was
charged with complex 1 (2.61 mg, 3.37 µmol), H2O (0.4 µL, 22 µmol),
Ph3CH (54 µL, 0.1743 M) as an internal standard, and C6D6 (ca. 0.6
mL). Complex 1 was consumed within approximately 5 min to produce
(TTP)TidO (3.37 µmol, 100%) and 1,1-dimethylhydrazine (3.34 µmol,
99%).
Reaction of (TTP)TidNNPh2 with Water. An NMR tube was
charged with complex 2 (8.54 mg, 9.50 µmol), H2O (0.4 µL, 22 µmol),
Ph3CH (50 µL, 0.1743 M) as an internal standard, and C6D6 (ca. 0.6
mL). After the tube was allowed to stand at ambient temperature for
Reaction of (TTP)TidNNMe2 with p-Chlorobenzaldehyde. An
NMR tube was charged with complex 1 (12.8 mg, 9.90 µmol),
p-chlorobenzaldehyde stock solution (7.0 µL, 1.726 M, 12.1 µmol),
Ph3CH (89 µL, 0.1814 M) as an internal standard, and C6D6 (ca. 0.5
mL). After the mixture was allowed to stand overnight at ambient
temperature, (TTP)TidO (9.43 µmol, 95%) and the hydrazone11 (7.74
µmol, 82%) were detected. GC-MS of p-chlorobenzaldehyde N,N-
1
44 h, (TTP)TidO (9.44 µmol, 99%) was detected by H NMR. The
free hydrazine was not quantified because of decomposition.
Reaction of (TTP)TidNiPr with Nitrosobenzene. An NMR tube
was charged with (TTP)TidNiPr (4.61 mg, 5.96 µmol), PhNO (0.8
mg, 7.47 mmol), Ph3CH (91 µL, 0.1448 M) as an internal standard,
and C6D6 (ca. 0.6 mL). After approximately 5 min at ambient
temperature quantitative production of (TTP)TidO and PhNdNiPr13
was observed. GC-MS of PhNdNiPr, Calcd (found) [M+]: 148.21(149)
m/z. 1H NMR of PhNdNiPr (CDCl3): δ 7.35 (t, 2H, m-PhNNiPr), 7.19
(t, 1H, p-PhNNiPr), 6.68 (d, 2H, o-PhNNiPr), 3.88, (spt, 1H, PhNNiPr),
1.24 (d, 6H, PhNNiPr).
1
dimethylhydrazone, Calcd (found) [M+]: 182.65 (182) m/z. H NMR
of (TTP)TidO (C6D6, 300 MHz): δ 9.24 (s 8H, â-H), 8.00 (m, 8H,
1
o-C6H4Me), 7.28 (m, 8H, m-C6H4Me), 2.42 (s, 12H, CH3). H NMR
of p-chlorobenzaldehyde N,N-dimethylhydrazone in C6D6 (300 MHz):
δ 7.39 (d, 2H, -C6H4Cl), 7.14 (d, 2H, -C6H4Cl), 6.80 (s, 1H, Nd
CH), 2.52 (s, 6H, CH3).
Reaction of (TTP)TidNNPh2 with p-Chlorobenzaldehyde. An
NMR tube was charged with complex 2 (4.95 mg, 5.51 µmol),
p-chlorobenzaldehyde stock solution (4.2 µL, 1.726 M, 7.25 µmol),
Ph3CH (92.6 µL, 0.1814 M) as an internal standard, and C6D6 (ca. 0.6
mL). The mixture was allowed to stand at ambient temperature for
180 h at which time (TTP)TidO (5.23 µmol, 95%) was observed. The
hydrazone12 could not be quantified because of the interfering internal
standard and porphyrin signals. GC-MS of p-chlorobenzaldehyde N,N-
diphenylhydrazone, Calcd (found) [M+]: 306.79 (307) m/z.
Results and Discussion
Synthesis and Properties of Hydrazido(2-) Complexes.
Treatment of the dichloro complex (TTP)TiCl2 with a 1,1-
disubstituted hydrazine in hexanes in the presence of a base
(eq 1) afforded the hydrazido complexes (TTP)TidNNR2 (R
Reaction of (TTP)TidNiPr with p-Chlorobenzaldehyde. An NMR
tube was charged with complex 3, (TTP)TidNiPr, (6.8 mg, 8.76 µmol),
p-chlorobenzaldehyde (3.8 mg, 27 µmol), Ph3CH (93.5 µL, 0.1743 M)
as an internal standard, and CDCl3 (ca. 0.6 mL). Allowing the tube to
stand at ambient temperature for 20 h produced (TTP)TidO (8.76 µmol,
i
100%) and PrNdCH(C6H4-p-Cl) (8.76 µmol, 100%). GC-MS of
p-chlorobenzylidene isopropylamine, Calcd (found) [M+]: 181.66 (182)
m/z. 1H NMR (CDCl3): δ 8.25 (s, 1H, NdCH), 7.65 (d, 2H, ClC6H4),
7.36 (d, 2H, ClC6H4), 3.54 (m, 1H, NCH(Me)2), 1.26 (d, 6H, NCH-
(Me)2).
Reaction of (TTP)TidNNMe2 with Phenol. An NMR tube was
charged with complex 1 (7.3 mg, 9.43 µmol), phenol (16 µL, 1.23 M,
19.68 µmol), Ph3CH (96 µL, 0.1743 M) as an internal standard, and
C6D6 (ca. 0.6 mL). Complex 1 was consumed within approximately 5
min to produce (TTP)Ti(OPh)2 (9.43 µmol, 100%) and 1,1-dimethyl-
hydrazine (9.83 µmol, 100%). 1H NMR of (TTP)Ti(OPh)2 in C6D6 (300
) Me (1), Ph (2)). In the absence of a base, a 1:1 mixture of
the hydrazido complex 1 and the 1,1-dimethylhydrazonium salt
was observed by 1H NMR. It was not possible to cleanly
separate the two products in large-scale reactions. When bases
such as triethylamine, picoline, pyridine, 1,2,3,4-tetrahydro-
quinoline, and 2,2,6,6-tetramethylpiperidine were used, the
solubilities of the hydrazido complexes and the ammonium salts
were similar and impeded purification. Piperidine was found
to be an adequate but not ideal base because separating the
piperidinium salt from the product still proved to be difficult
and resulted in modest isolated yields (20-50%) of the
hydrazido complexes. Alternative routes, such as the use of
LiNHNR2 or H2N2R2 in the presence of LinBu as well as other
(11) 1H NMR of an authentic sample of p-chlorobenzaldehyde N,N-
dimethylhydrazone (CD2Cl2, 300 MHz): δ 7.48 (d, 2H, p-ClC6H4C(H)-
NNMe2), 7.28 (d, 2H, p-ClC6H4C(H)NNMe2), 7.15 (s, 1H,
p-ClC6H4C(H)NNMe2), 2.95 (s, 6H, p-ClC6H4C(H)NNMe2). Wiley,
R. H.; Slaymaker, S. C.; Kraus, H. J. Org. Chem. 1957, 22, 204.
(12) Kamitori, Y.; Hojo, M.; Masuda, R.; Fujitani, T.; Ohara, S.; Yokoyama,
T. J. Org. Chem. 1988, 53, 129.
(13) Seyhan, N. E.; Sharp, R. R. J. Chem. Soc. B 1971, 2014.

Ti(IV) Tetratolylporphyrin
Inorganic Chemistry, Vol. 39, No. 6, 2000 1303
1
reaction solvents, led only to intractable paramagnetic products.
Attempted synthesis of a diazenoid species from 1,2-diphenyl-
hydrazine in the presence of piperidine also led to intractable
paramagnetic products. Although complex 2 was robust in
solution at elevated temperatures (ca. 350 K), complex 1 was
not and decomposed to paramagnetic species, as indicated by
1H NMR spectroscopy.
quantitative yield as monitored by H NMR (eq 4). Reactions
Because of the large ring current of the porphyrin macrocycle,
the 1H NMR resonances associated with the substituents on the
bound hydrazido ligand were significantly shifted upfield
relative to the hydrazine. For complex 1, the methyl resonance
was shifted upfield approximately 2.5 ppm from that of the free
hydrazine. The phenyl signals for complex 2 were similarly
shifted upfield. For example, the o-NNPh2 proton doublet (4.34
ppm) found for 2 was shifted upfield from the free hydrazine
(7.11 ppm). The 1H NMR spectra showed that the substituents
on the hydrazido(2-) moiety were equivalent on the NMR time
scale (223-300 K). This observation supported the formulation
of the hydrazido(2-) unit as an η1-bound ligand.
with a larger ratio of the aldehyde to hydrazido complex
proceeded to completion over a shorter period of time. The
reaction rate of the diphenylhydrazido complex 2 with aldehyde
was qualitatively slower than that of the dimethyl analogue 1.
This was consistent with a less nucleophilic NR of the hydrazido
moiety in complex 2.
Reactivity of (TTP)TidNiPr. Although (TTP)TidNiPr, 3,
did not undergo nitrene transfer in the presence of a variety of
substrates such as OPR3, OAsPh3, RNCNR, and R2CO, it did
undergo nitrene metathesis reactions with nitroso compounds.
Facile and quantitative production of the unsymmetric diazene
compound PhNdNiPr resulted from reaction of complex 3 with
nitrosobenzene (eq 5). Low-valent titanium complexes have been
In the presence of water or phenol, both complexes 1 and 2
were converted to (TTP)TidO or (TTP)Ti(OPh)2, respectively,
and to the appropriate 1,1-disubstituted hydrazine (eqs 2 and
3).14 As is generally the case for disubstituted hydrazido(2-)
found to mediate the coupling of nitrene groups derived from
nitroso compounds.16,17 It was proposed that these reactions
progressed through two different bimetallic intermediates in
order to explain the presence of azo- and azoxy-coupling
products. In the case presented here we conclude that the diazene
product is produced from a monomeric intermediate in which
the nitrosobenzene is bound to the titanium cis to the imido
group. Nitrosobenzene has been used as a trapping agent for
reactive rhodium18 and palladium19 nitrene intermediates to
produce azoxybenzene.16b If an azoxybenzene were formed from
the reaction of complex 3 with PhNO, it would likely be reduced
rapidly to a diazene by the coproduct (TTP)Ti(II). The nucleo-
philic character of nitrene groups has often been displayed by
reaction with aldehydes.20 Zr imido complexes have previously
been demonstrated to convert ketones and aldehydes to imines.21
Likewise, the reaction of complex 3 with three equiv of
p-chlorobenzaldehyde at 20 °C produced (TTP)TidO and
p-chlorobenzylidene isopropylamine in 20 h. In the presence
of only 1 equiv of aldehyde, complete consumption of the imido
complex required approximately 4 weeks.
complexes, N-N bond cleavage was not observed in these
protonolysis reactions.15 The extreme hydrolytic susceptibility
of complex 1 precluded a satisfactory elemental analysis, while
complex 2 was found to be somewhat more inert. In the presence
of approximately 1 equiv of phenol, a 1:1 mixture of the bis-
(phenoxide), (TTP)Ti(OPh)2, and unreacted hydrazido, 2, was
present.
Exchange of the NNR2 group was not observed upon
treatment of (TTP)TidNNR2 with free hydrazine H2N2R′2 (R
) Me, R′ ) Ph; R ) Ph, R′ ) Me). The protonation of
complexes 1 and 2 was not detected in the presence of excess
HNPh2 or H2NPh. This is in line with the higher acidity of
hydrazines relative to amines. Consequently, the potentially
direct route to complexes 1 and 2 by treatment of the imido
compound 3 with the respective hydrazine was unproductive.
The hydrazido and imido complexes were only minor compo-
nents in an otherwise intractable mixture of products. This is
in contrast to the tetramethyltetraazaannulene analogues,
(TMTAA)TidNR, which cleanly produce hydrazido(2-) com-
plexes on treatment with H2NNR2.7
Conclusion
The (TTP)TidNNR2 complexes were investigated in an effort
to further elucidate the reactivity of the titanium-nitrogen
double bond found in metalloporphyrin complexes. The hy-
Treatment of complexes 1 or 2 with approximately 1 equiv
of p-chlorobenzaldehyde slowly produced the hydrazone p-Cl-
C6H4C(NNR2)H (R ) Me, Ph) and (TTP)TidO in nearly
(16) The chemistry of nitrosobenzene has been reveiwed. (a) Zuman, P.;
Shah, B. Chem. ReV. 1994, 94, 1621. (b) Cameron, M.; Gowenlock,
B. G.; Vasapollo, G. Chem. Soc. ReV. 1990, 19, 355.
(17) Fochi, G.; Floriani, C. J. Chem. Soc., Dalton Trans. 1984, 2577.
(18) Ragaini, F.; Cenini, S.; Demartin, F. Organometallics 1994, 13, 1178.
(19) Eremenko, I. L.; Nefedov, S. E.; Sidorov, A. A.; Ponina, M. O.;
Danilov, P. V.; Stromnova, T. A.; Stolarov, I. P.; Katser, S. B.; Orlova,
S. T.; Vargaftik, M. N.; Moiseev, I. I.; Ustynyuk, Y. A. J. Organomet.
Chem. 1998, 551, 171.
(14) (a) Woo, L. K.; Hayes, J. A.; Goll, J. G. Inorg. Chem. 1990, 29, 3916.
(b) Gray, S. D.; Thorman, J. L.; Berreau, L. M.; Woo, L. K. Inorg.
Chem. 1997, 36, 278.
(15) (a) Chatt, J.; Crichton, B. A. L.; Dilworth, J. R.; Dahlstrom, P.;
Gutkoska, R.; Zubeita, J. Inorg. Chem. 1982, 21, 2383. (b) Bustos,
C.; Manzur, C.; Carrillo, D.; Robert, F.; Gouzerh, P. Inorg. Chem.
1994, 33, 1427. (c) For exceptions see the following. Niemoth-
Anderson, J. D.; Debord, J. R. D.; George, T. A.; Ross, C. R.;
Stezowski, J. J. Polyhedron 1996, 15, 4031 and references therein.
(20) Arndtsen, B. A.; Sleiman, H. F.; Chang, A. K.; McElwee-White, L.
J. Am. Chem. Soc. 1991, 113, 4871 and references therein.
(21) Lee, S. Y.; Bergman, R. G. J. Am. Chem. Soc. 1996, 118, 6396.

1304 Inorganic Chemistry, Vol. 39, No. 6, 2000
Thorman and Woo
drazido complexes exhibited behavior similar to that of the imido
species (TTP)TidNiPr in the presence of protic reagents. Nitrene
group transfer from the titanium imido complex, (TTP)TidNiPr,
resulted from treatment with p-chlorobenzaldehyde or ni-
trosobenzene to yield the respective imine or diazene. The
hydrazido derivatives also reacted with p-chlorobenzaldehyde
to form the subsequent hydrazone. These results show that by
reducing the steric constraint at the NR of the nitrene group,
the metalloporphyrin TidN moiety exhibits moderate reactivity.
Acknowledgment. We are grateful for financial support from
the Camille and Henry Dreyfus Foundation.
IC990991L