Titanium complexes of dialkanolamine ligands: Synthesis and structure

Article abstract of DOI:10.1002/ejic.200501154

Synthesis of the title compounds, viz. [RN(CH₂CH ₂O)-(CHR¹CR²R³O)]Ti(OiPr) ₂ (13-15) and [RN(CH₂CH₂O)-(CHR ¹CR²R³O)]₂Ti (18

Full text of DOI:10.1002/ejic.200501154

FULL PAPER
DOI: 10.1002/ejic.200501154
Titanium Complexes of Dialkanolamine Ligands: Synthesis and Structure
Kirill V. Zaitsev,[a] Sergey S. Karlov,*[a] Anastasia A. Selina,[a] Yu. F. Oprunenko,[a]
Andrei V. Churakov,[b] Bernhard Neumüller,[c] Judith A. K. Howard,[d] and
Galina S. Zaitseva[a]
Keywords: Titanium / Alkoxides / Pentacoordination / Hexacoordination / Dialkanolamine complexes
Synthesis of the title compounds, viz. [RN(CH2CH2O)-
(CHR1CR2R3O)]Ti(OiPr)2 (13–15) and [RN(CH2CH2O)-
(CHR1CR2R3O)]2Ti (18–28), by the reaction of one or
two equivalents of the corresponding dialkanolamines
RN(CH2CH2OH)(CHR1CR2R3OH) (1–12) with Ti(OiPr)4 is re-
ported. Other routes to [RN(CH2CH2O)(CHR1CR2R3O)]2Ti,
such as the reaction of Ti(CH2Ph)4 with dialkanolamine and
the reaction of TiCl4(THF)2 with dialkanolamine/Et3N were
also tested. Dimeric titanocane 16, [PhCH2N(CH2CH2O)2Ti-
(OMe)2]2, was obtained from the reaction of one equivalent
of dialkanolamine 3 with CpTi(OMe)3. PhCH2N(CH2CH2O)2-
Ti(OMenth)2 (17) was prepared from the transalkoxylation
reaction of 15 with two equivalents of menthol. The composi-
tion and structures of all novel compounds were established
by 1H and 13C NMR spectroscopy as well as elemental analy-
sis data. The possible solution structure features of 13–28 are
discussed. The single-crystal X-ray diffraction study of
titanocane 16 clearly indicates a dimeric structure for this
compound in the solid state. According to X-ray data, com-
pounds [PhCH2N(CH2CH2O)2]2Ti (19), [MeN(CH2CH2O)-
(CH2CHPhO)]2Ti (20), [MeN(CH2CH2O)(CH2CPh2O)]2Ti
(23), erythro-[MeN(CH2CH2O)(CHPhCHPhO)]2Ti (24), threo-
[MeN(CH2CH2O)(CHPhCHPhO)]2Ti (25), and {MeN(CH2-
CH2O)[CH(CH2)4CHO]}2Ti (27) possess a monomeric struc-
ture with a hexacoordinate titanium atom in the solid state.
Among them complexes 19, 20, 23, 25, and 27 are charac-
terized by a cis disposition of the nitrogen atoms in the coor-
dination environment of the Ti atom, while nitrogen atoms in
24 occupy trans positions.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
R3O)2Ti(X)XЈ, are less studied.[20–26] However, this class of
compounds could be more promising for investigations be-
cause of their greater chemical and structural flexibility. In
addition, some cyclic titanium alkoxides with transannular
interactions were recently found to be good catalysts in ole-
fin polymerization reactions.[27–33]
Introduction
Alkoxy- or aroxytitanium derivatives have attracted the
attention of researchers during the last five decades because
of their possible application as catalysts in various organic
reactions,[1–8] as well as precursors for titanium sol-gel
chemistry[9] and metal-organic chemical vapor deposition
(MOCVD) processes.[10] Among these species, the com-
pounds with different trialkanolamines, titanatranes,
N(CR1R4CR2R3O)3TiX, with different substituents at the
carbon atoms of the atrane skeleton, have been investigated
to a considerable extent because of their rich structural fea-
tures and catalytic activities including polymerization reac-
tions of alkenes (see key references and references cited
therein).[11–19] At the same time the closely related deriva-
tives of dialkanolamines, titanocanes, RN(CR1R4CR2-
As a part of our program to investigate the structure and
chemical behavior of metal complexes containing di- and
trialkanolamine ligands,[34–43] we present the study of reac-
tions of dialkanolamines 1–12 with Ti(OiPr)4. In the case
of the reaction of RN(CH2CH2OH)2 with Ti(OiPr)4 (1:1
ratio) novel titanocanes 13–15 formed (R = Ph, Me,
PhCH2). The dimer [PhCH2N(CH2CH2O)2Ti(OMe)2]2 (16),
was obtained from the reaction of dialkanolamine 3 with
CpTi(OMe)3. The reaction of 15 with two equivalents of
menthol led to PhCH2N(CH2CH2O)2Ti(OMenth)2 (17).
1,1Ј-Spirobititanocanes 18–28 of type [RN(CH2CH2O)-
(CHR1CR2R3O)]2Ti were prepared from the reaction of
two equivalents of the corresponding dialkanolamines with
Ti(OiPr)4. The solid state and solution structures of pre-
pared compounds are discussed on the basis of X-ray dif-
fraction and NMR spectroscopic data. Once this work had
been finished the report of Carpentier and coworkers was
published where the synthesis and structural investigations
of several closely related titanocanes and 1,1Ј-spirobititano-
canes were reported.[44]
[a] Chemistry Department Moscow State University,
B-234 Leninskie Gory, 119899 Moscow, Russia
Fax: +007-095-932-8846
E-mail: sergej@org.chem.msu.su
[b] Institute of General and Inorganic Chemistry, RAS,
Leninskii pr., 31, 119991 Moscow, Russia
[c] Fachbereich Chemie, Philipps-Universität Marburg,
Hans-Meerwein-Strasse, 35032 Marburg/Lahn, Germany
[d] Department of Chemistry, University of Durham,
South Road, DH1 3LE Durham, United Kingdom
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1987

S. S. Karlov et al.
FULL PAPER
action of two equivalents of dialkanolamine 2 with
Ti(OiPr)4 gave the bishomoleptic complex [MeN(CH2-
Results and Discussion
Dialkanolamines 1–12 were involved in this study. The CH2O)2]2Ti (29). This transformation was supposed to pro-
compounds 8–12 were obtained from the reaction of the ceed through a very reactive and unstable MeN(CH2-
corresponding alkene oxides with N-methylethanolamine in CH2O)2Ti(OiPr)2 but this suggestion was not confirmed by
high yields (Scheme 1). The reaction with indene oxide was any analytical methods.[20] Increasing the amount of
previously reported, but the structure of product 12 was Ti(OiPr)4 in the reaction mixture led to the unexpected
not discussed.[45] Compound 7 was previously prepared by [Ti2{µ2-(OCH2CH2)2NMe}(µ2-OiPr)(OiPr)5].[21] The analo-
another method.[46] Compounds 8–11 are novel.
gous species, Ti2(OCH2CH2NMe)2(OtBu)6, was prepared
The reactions proceeded regiospecifically, only one ex- by the reaction of Ti(OtBu)4 with 2.[22] The treatment of
pected product formed in the reactions with but-1-ene ox- Ti(OiPr)4 with one equivalent of 2 in the presence of one
ide, 1,1-diphenylethylene oxide, and indene oxide. Only one equivalent of different diols led to dimeric titanium amino-
diastereomer formed in the reactions with cis- and trans- alkoxydiolates, [MeN(CH2CH2O)2Ti(O-A-O)]2 (O-A-O =
stilbene oxides, as well as cyclopentene and cyclohexene ox- OCMe2CMe2O, OCEt2CEt2O, OCMe2CH2CMe2O, OC-
ides.
Me2CH2CHMeO). Dimerization in latter complexes is real-
Titanocanes: According to the literature, the most suit- ized by the interaction of the oxygen atom of one dialkanol-
able approach to the dialkoxy complexes of titanium with amine “arm” of one monomeric unit with the Ti atom of
chelate ligands is the transalkoxylation reaction of the other.[23] Lavanant et al. have found that the reaction of
Ti(OAlk)4 with the free ligand containing two OH groups. one equivalent of PhCH2N(CH2CMe2OH)2 with Ti(OiPr)4
This method was used in the case of the closely related li- gave the complex PhCH2N(CH2CMe2O)2Ti(OiPr)2, which
gands RN(CH2-o-ArOH)2, where o-Ar is a benzene ring is monomeric in the solid state and in solution ([D8]tolu-
with different alkyl (methyl or tert-butyl) substituents and ene).[44]
R is CH2CH2NMe2.[27] When R is nPr, the presence of an
We have found that dialkanolamines 1–3 reacted readily
alkyl group in the other ortho position to the OH group of with an equimolar amount of Ti(OiPr)4 at room tempera-
such ligands is required for the formation of bis(isopropox- ture in chloroform or toluene solution to give the corre-
ide) complexes, otherwise the formation of bishomoleptic sponding titanocanes 13–15 in high yields (Scheme 2). We
substances [RN(CH2-o-ArO)2]2Ti has been found.[27] Anal- also tested two other reactions that may lead to the titano-
ogous results were found for other structurally close canes, where X = XЈ. However, both reactions did not result
bis(phenols). The treatment of Ti(OAlk)4 (Alk = iPr, Me) in the desired products (Scheme 2). CpSn-nBu3, one of the
with one equivalent of the bis(phenol), CH2[(3-tBu-5- possible by-products in the reaction of Cp2TiCl2 with
MeC6H2)-2-OH]2, gave monomeric complexes with a tetra- MeN(CH2CH2OSn-nBu3)2, was detected by NMR spec-
coordinate Ti atom (NMR spectroscopic data), CH2[(3- troscopy.
tBu-5-MeC6H2)-2-O]2Ti(OAlk)2.[30] Reacting the thio-bis-
Our efforts to prepare titanocane with different substitu-
(phenol), S[(3-tBu-5-MeC6H2)-2-OH]2, with Ti(OiPr)4 re- ents X and XЈ by the transalkoxylation reaction of dialkan-
sulted in the dimeric [S[(3-tBu-5-MeC6H2)-2-O]2Ti(OiPr)2]2 olamine 3 with (MeO)3TiCp failed. Only the dimer 16
(X-ray data) where dimerization ensues from the interaction was obtained. In contrast, Kim et al. synthesized
of the oxygen atom of the isopropoxy group of one mono- RN(CH2CH2O)2Ti(Cl)Cp* by the reaction of Cl3TiCp*
meric unit with the Ti atom of the other.[31] The diisopro- (where Cp*
=
pentamethylcyclopentadienyl) with
poxy titanium complexes based on diamino-dialkoxide li- RN(CH2CH2OH)2 (R = Me, nBu).[25] We believe that the
gands, [-CH2N(Me)CH2C(CF3)2OH]2 and CH2[CH2N- difference in the behavior of (MeO)3TiCp and Cl3TiCp*
(Me)CH2C(CF3)2OH]2, were also recently prepared by (the rupture of Ti–Cp bond and the stability of Ti–Cp*
Carpentier and coworkers by the transalkoxylation reaction bond in the course of the reaction) is because of the dif-
of Ti(OiPr)4.[32]
ferent properties of these bonds.
To the best of our knowledge, the reactions of dialkanol-
The possibility of alkoxy groups exchanging at the tita-
amines with Ti(OiPr)4 have only been published in a series nium atom was confirmed by the formation of complex 17
of works by Kemmitt et al. and very recently in the report in the reaction of diisopropoxy derivative 15 with -(–)-
of Lavanant et al.[20–23,44] Kemmitt et al. noted that the re- menthol (Scheme 2).
Scheme 1.
1988
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Titanium Complexes of Dialkanolamine Ligands
FULL PAPER
the titanium atom, gave crystals suitable for an X-ray dif-
fraction study. The molecular structure of 16 is shown in
Figure 1. Table 1 lists selected geometrical parameters for
16. The molecule of 16 represents a centrosymmetric com-
plex with a Ti2O2 lozenge. The dimer results from µ2-bridg-
ing by one methoxy group of one monomeric unit. The di-
ethanolamine ligands in each dimer are bound meridionally
to each titanium atom. Of interest, all previously studied
alkoxytitanocanes except PhCH2N(CH2CMe2O)2Ti(OiPr)2
are also dimeric, but the dimerization results from µ2-bridg-
ing by one alkoxy “arm” of the diethanolamine ligand.[23,44]
The coordination polyhedron of the Ti atoms in compound
16 represents a distorted octahedral geometry with the N(1)
atom and O(4) atom (nonbridging methoxy group) in a
trans orientation. The Ti(1)–N(1) distance in 16 [2.355(2) Å]
is close to that previously found for [MeN(CH2CH2O)2-
Ti(O-A-O)]2 [2.351(4)–2.431(4) Å].[23] The longest Ti–O dis-
tances in 16 [Ti(1)–O(3A) 2.024(1); Ti(1)–O(3) 2.066(1) Å]
correspond to the bonds of titanium with both bridging
methoxy groups, as expected. All five-membered rings of
the ocane skeletons in 16 adopt an envelope-like conforma-
tion, all carbon atoms in the α positions to the N atom
occupy “flap” sites, while the C-β atoms form the base of
these envelope planes.
Scheme 2.
One of the most important questions in the chemistry of
titanium is the coordination state of the Ti atom both in
the solid state and in solutions. In our opinion the type of
coordination environment around the titanium atoms is
very important because of the potential ability of these
compounds to catalyze different organic reactions where
the stereochemistry of the catalytic center is significant.[3–8]
Titanocanes prepared by us may possess monomeric struc-
tures with pentacoordinate titanium atoms or dimeric struc-
tures with hexacoordinate titanium atoms. There are two
possibilities for dimerization: through the dialkanolamine
moiety or through the alkoxy groups. According to the lit-
erature, most of the titanocanes prepared to date,
[MeN(CH2CH2O)2Ti(O-A-O)]2 (O-A-O = OCMe2CMe2O,
OCEt2CEt2O,
OCMe2CH2CMe2O,
OCMe2CH2CH-
Figure 1. Molecular structure of 16. Hydrogen atoms and solvate
MeO),[23] are dimeric in the solid state. The dimerization is
realized by the additional contact of the oxygen atom of
one diethanolamine “arm”. In CDCl3 solutions two com-
pounds are also dimeric at room temperature (O-A-O =
OCMe2CMe2O, OCEt2CEt2O) while two others are mono-
meric (O-A-O = OCMe2CH2CMe2O, OCMe2CH2CH-
MeO).[23] PhCH2N(CH2CMe2O)2Ti(OiPr)2 is monomeric
dichloromethane molecules are omitted for clarity.
Table 1. Selected bond lengths [Å] and angles [°] for 16.
Ti(1)–O(4)
Ti(1)–O(1)
Ti(1)–O(2)
Ti(1)–O(3A)
1.808(1)
1.868(1)
1.873(1)
2.024(1)
2.066(1)
2.355(2)
O(4)–Ti(1)–N(1)
O(1)–Ti(1)–N(1)
O(2)–Ti(1)–N(1)
O(3A)–Ti(1)–N(1)
O(3)–Ti(1)–N(1)
162.26(6)
75.59(6)
76.79(6)
94.03(5)
92.07(5)
in the solid state and in solution (toluene-d8).[44] As cited Ti(1)–O(3)
above, the closely related derivatives, nPrN{CH2[3,5-
Ti(1)–N(1)
bis(tBu)-C6H2]-2-O}2Ti(OiPr)2 and nPrN{CH2[3,5-bis-
(Me)-C6H2]-2-O}2Ti(OiPr)2, are monomeric both in the so-
1H and 13C NMR spectroscopic data (CDCl3 solution,
room temperature) of 16 are in agreement with the centro-
lid state and in solution (C6D6).[27]
Among five dialkoxytitanocanes prepared by us only one symmetric dimeric solid-state structure. In the 1H NMR
compound 16, the titanocane with two methoxy groups at spectrum of 16 there are two singlets of methoxy groups.
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S. S. Karlov et al.
FULL PAPER
The signals of the methylene protons of one ocane skeleton canes is the determining factor that governs the coordina-
appear as a set of multiplets resulting from the nonequiva- tion number in titanocanes.
lence of all protons. Separate 13C NMR signals were found
Spirobititanocanes: Only two spirobititanocanes were re-
for each carbon of the diethanolamine ligand in 16. On the ported by the beginning of our investigation, one of them
contrary, two other titanocanes with the benzyl group at is [MeN(CH2CH2O)2]2Ti (29).[20] Very recently the synthe-
the nitrogen atom (15 and 17) are monomeric in CDCl3 sis of [PhCH2N(CH2CMe2O)2]2Ti from the reaction of
solution at room temperature. This conclusion is based on Ti(OiPr)4 with two equivalents of corresponding dialkanol-
the presence of one signal of the OCH2 group and one sig- amine was reported.[44] For synthesis of 29 the treatment of
nal of the NCH2 group for the C atoms of the ocane skel- two equivalents of dialkanolamine 2 with Ti(OiPr)4 or
eton of these compounds. Thus, these species (15 and 17) freshly prepared α-titanic acid was used. The structure of
possess monomeric structures with trigonal-bipyramidal 29 was confirmed by X-ray diffraction, this species is mono-
coordination environments of the titanium atom. These meric in the solid state. The coordination polyhedron of the
compounds may undergo exchange processes in solution Ti atom represents a distorted octahedral geometry with
(the exchange between equatorial and axial alkoxy two nitrogen atoms in a cis orientation (Scheme 3).[20] We
1
groups).[44] Thus, the drastic difference in H NMR spectra have very recently found an analogous situation in spirobi-
of 15 (OCH protons of the isoproxy group represent one germocanes. Both [PhN(CH2CH2O)2]2Ge and [MeN(CH2-
broad singlet) and 17 (OCH protons of two menthoxy CH2O)(CH2CHPhO)]2Ge possess the structure of the cis
groups represent two spaced multiplets), to our opinion, re- isomer.[34] The bishomoleptic titanium derivative, {S[(3-
sulted from the different dynamic behavior of these com- tBu-5-MeC6H2)-2-O]2}2Ti, has an analogous structure.[47]
pounds in solution. While isopropoxy groups in 15 undergo Lavanant et al. supposed that the monomeric structure is
fast position exchange around the Ti atom, more bulky present in solution for [PhCH2N(CH2CMe2O)2]2Ti.[44]
menthoxy groups in 17 resulted in the rigid structure of
the molecule. It should be noted that previously prepared
PhCH2N(CH2CMe2O)2Ti(OiPr)2 demonstrated the same
trends in the NMR spectra as compound 15.[44] The au-
thors concluded that
a
monomeric structure of
PhCH2N(CH2CMe2O)2Ti(OiPr)2 occurs. This conclusion
was also supported by variable temperature NMR spec-
troscopy.[44] The structure of diisopropoxytitanocane 14 is
close to that of 15 according to the NMR spectroscopic
data. In the 13C spectrum of 13 the broadening of each
Scheme 3.
The closely related spiro-bishomoleptic or spiro-bisheter-
signal is observed, probably because of possible monomer- oleptic complexes of titanium were prepared by Tshuva et
dimer interconversion in this compound. Thus we can con- al. by the reaction of nPrN(CH2-o-ArOH)2 or RN(CH2-o-
clude that the steric bulkiness of alkoxy ligands in titano- ArЈOH)2 (R = nPr or CH2CH2NMe2) with Ti(OiPr)4 lead-
Scheme 4.
1990
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Titanium Complexes of Dialkanolamine Ligands
FULL PAPER
ing to [nPrN(CH2-o-ArO)2]2Ti or [nPrN(CH2-o-ArO)2] hand, the symmetric bis(ocanes) are more thermodynami-
Ti[(O-o-ArЈ-CH2)2NR], respectively.[27] Three complexes cally stable in the case of dialkanolamine type ligands. On
were studied by X-ray diffraction and showed the structure the other hand, the unsymmetric bis(ocanes) are probably
of trans-isomer A (Scheme 3). The authors noted that the formed in the course of the reactions, but because of their
bulky substituents in the Ar groups prevent the formation higher flexibility in comparison with that for phenolic spe-
of spiro-bishomoleptic species and the reaction stops at the cies[27] a mixture of symmetric compounds forms through
titanocanes.[27] An analogous result in Zr chemistry has a metathetical process.
been found by Mountford and coworkers.[33] A very inter-
One dialkanolamine ligand in spirobititanocane 18 can
esting result was found by Lavanant et al. for Zr derivatives easily be exchanged by the treatment with equimolar
of two dialkanolamines: [PhCH2N(CH2CMe2O)2]2Zr and amounts of Ti(OiPr)4 (Scheme 6). The reaction of 19 with
[PhCH2N(CH2C-p-Tol2O)2]2Zr.[44] According to the NMR one equivalent of TiCl4 resulted in a mixture of unidentified
spectroscopic data both spirobizirconocanes are monomeric products (Scheme 6).
in solution while the X-ray diffraction study of
[PhCH2N(CH2CMe2O)2]2Zr showed the dimeric structure
of this compound in the solid state resulting from the rup-
ture of three of the four Zr–N bonds into two monomeric
units.[44] Thus, one can conclude that the structure of the
ligand is the main factor governing the coordination envi-
ronment around the metal atom in spirobiocanes.
In order to clarify the structure of the ligand influence
we explored the synthesis and structures of the number of
novel spirobititanocanes. The compounds 18–28 were ob-
tained in high yields from the reaction of Ti(OiPr)4 with
two equivalents of corresponding dialkanolamines 1, 3–12
at reflux in toluene (Scheme 4). Compound 19 was also pre-
pared in 33% yield from the treatment of TiCl4·(THF)2
with 3 in the presence of Et3N or in quantitative yield from
Scheme 6.
the reaction of Ti(CH2Ph)4 with two equivalents of 3
(Scheme 4). The latter approach was also used for the syn- ocane 19 possesses a monomeric structure in solution
thesis of 23. (CDCl3) and exists as one isomer (Scheme 3). It should be
According to the NMR spectroscopic data, spirobititan-
We also tried to prepare spiro-bisheteroleptic ocanes noted that in the trans and cis isomers of 19 the two dialk-
(Scheme 5), but in all of the studied cases equimolar mix- anolamine groups are equivalent. Thus, in theory it is im-
tures of spiro-bishomoleptic ocanes were obtained (NMR possible to define what kind of isomer exists in CDCl3 solu-
spectroscopic data). This result contradicts that previously tion, but we can conclude that only one isomer is present
found for bis(aminophenol)-type ligands, where the bishet- under these conditions. We believe that spirobititanocane
eroleptic species are stable.[27] We suppose that, on the one 18 is also monomeric in solution, but the broadening of
Scheme 5.
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S. S. Karlov et al.
FULL PAPER
signals was found for its NMR spectra (like in closely re- though different sets of signals should be present in the 13
C
lated titanocane 13). This indicates the presence of dynamic NMR spectra of the trans and cis isomers for compound
processes in solution of 18, such as Berry pseudorotation, 20–28, it is very difficult to determine unambiguously the
cis-trans isomerization and/or N–Ti bond dissociation. Al- type of isomer in this case because of the presence of several
diastereomers of these compounds in solution resulting
from the asymmetric carbon atoms. However, the impor-
tance of the synthesis of compounds with asymmetric car-
Figure 2. Molecular structure of 19 (one independent molecule).
Hydrogen atoms are omitted for clarity.
Figure 4. Molecular structure of 23. Hydrogen atoms and solvate
dichloromethane molecules are omitted for clarity.
Figure 3. Molecular structure of 20. Hydrogen atoms and solvate
toluene molecules are omitted for clarity.
Figure 5. Molecular structure of 24. Hydrogen atoms and solvate
toluene molecules are omitted for clarity.
1992
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Titanium Complexes of Dialkanolamine Ligands
FULL PAPER
Figure 7. Molecular structure of 27. Hydrogen atoms are omitted
for clarity.
Figure 6. Molecular structure of 25. Hydrogen atoms and solvate
Table 3. Selected bond lengths [Å] and angles [°] for 24.
dichloromethane molecules are omitted for clarity.
Ti(1)–N(1)
Ti(1)–N(2)
Ti(1)–O(11)
Ti(1)–O(12)
Ti(1)–O(21)
Ti(1)–O(22)
O(12)–Ti(1)–O(22) 102.1(1)
O(12)–Ti(1)–O(11) 145.0(1)
O(22)–Ti(1)–O(11) 95.0(1)
2.339(2)
2.310(2)
1.878(2)
1.864(2)
1.883(2)
1.873(2)
O(12)–Ti(1)–O(21) 95.6(1)
O(22)–Ti(1)–O(21) 146.1(1)
O(11)–Ti(1)–O(21) 86.41(9)
O(12)–Ti(1)–N(1) 74.34(9)
O(22)–Ti(1)–N(1) 93.17(9)
O(11)–Ti(1)–N(1) 74.39(8)
O(21)–Ti(1)–N(1) 119.57(8)
bon atoms is connected with the usefulness of these deriva-
tives in catalytic processes.
The structures of six spirobititanocanes 19, 20, 23, 24,
25, 27 were studied by X-ray diffraction. The monomeric
nature of all the studied species with a hexacoordinate tita-
nium center was confirmed. The coordination polyhedron
of the titanium atom in these compounds represents a dis-
torted octahedron. The molecular structures of 19 (one in-
N(2)–Ti(1)–N(1)
162.91(8)
The compounds 19, 20, 23, 25, and 27 exhibit a cis dispo-
dependent molecule), 20, 23, 24, 25, and 27 are shown in sition of the two nitrogen atoms at the Ti atom. An analo-
Figure 2, Figure 3, Figure 4, Figure 5, Figure 6, and Fig- gous structure was previously found in 29.[20] On the con-
ure 7, respectively. Table 2 and Table 3 list selected geomet- trary, the nitrogen atoms in 24 occupy the trans positions
rical parameters for these compounds.
in an octahedral environment of the Ti atom. This type of
Table 2. Selected bond lengths [Å] and angles [°] for 19, 20, 23, 25, 27.
19
20
23
25
27
Ti–N
2.451(2)
2.467(2)
1.830(2)
1.844(2)
2.352(2)
2.367(2)
1.855(2)
1.862(2)
1.875(2)
1.885(2)
75.66(7)
75.88(7)
82.31(7)
163.95(7)
117.58(7)
92.38(7)
98.95(7)
99.17(7)
110.72(7)
111.40(7)
136.17(8)
2.357(2)
2.363(2)
2.471(3)
Ti–Otrans to N
Ti–Otrans to O
N(1)–Ti–O
1.839(2)
1.852(2)
1.865(1)
1.859(1)
1.872(2)
1.867(2)
1.849(2)
1.845(3)
73.40(7)
75.87(7)
83.15(7)
163.61(7)
118.1(1)
91.9(1)
101.50(8)
110.35(8)
133.7(1)
74.55(9)
75.52(8)
81.94(8)
164.91(8)
117.8(1)
92.4(1)
101.9(1)
109.8(1)
133.7(1)
73.68(5)
75.46(6)
82.34(6)
154.98(5)
129.69(8)
85.33(8)
102.89(6)
116.23(6)
126.24(9)
74.55(6)
75.12(7)
82.15(7)
158.18(7)
125.37(9)
87.68(9)
101.81(7)
114.44(7)
129.2(1)
74.1(1)
75.2(1)
81.7(1)
161.9(1)
120.5(1)
91.2(2)
101.4(1)
113.3(1)
130.0(2)
N–Ti–N
O–Ti–O
Eur. J. Inorg. Chem. 2006, 1987–1999
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1993

S. S. Karlov et al.
FULL PAPER
structure is considered to be trans-isomer B (Scheme 3). To
the best of our knowledge, compound 24 is the first exam-
ple of such a structure; however, a similar trans disposition
of the nitrogen atoms in TiO4N2 was previously found.[48]
The Ti–N distances in 19, 20, 23, 24, 25, and 27 vary
over the range 2.310(2)–2.471(3) Å, the shortest distance
being found in compound 24 (trans disposition of N
atoms). These values are close to that previously found for
29 [2.422(2) Å].[20] The substitution of hydrogen atoms (19,
29) of the ocane skeleton for phenyl groups (20, 23, 24, 25)
shortens the Ti–N bond, while the substitution with alkyl
groups (27) slightly elongates this distance. In general, the
Ti–N distances in phenolic compounds [nPrN(CH2-o-ArO)2]-
Ti[(O-o-ArЈCH2)2NR] [2.248(2)–2.308(4) Å][27] are shorter
than those in 19, 20, 23, 24, 25, 27, and 29 based on dialk-
anolamine-type ligands. This difference is probably ex-
plained by the higher polarity of the Ti–O bonds in pheno-
lic species, which leads to depletion of electron density at
the titanium center. A similar tendency was found for Ti–
O bonds in hexacoordinate compounds discussed above. In
general, the shorter Ti–N bonds in the molecules corre-
spond to longer Ti–O bonds. This tendency is also sup-
ported by the fact that Ti–O bonds in the only X-ray
studied monomeric tetraalkoxy titanium derivative with a
tetracoordinate Ti atom [1.752(2)–1.825(2) Å][49] are con-
siderably shorter than those in the hexacoordinate com-
pounds.
Experimental Section
General Remarks: All manipulations were performed under a dry,
oxygen-free argon atmosphere using standard Schlenk techniques.
Solvents were dried by standard methods and distilled prior to use.
PhN(CH2CH2OH)2 (1), MeNHCH2CH2OH (Aldrich) and
(1R,2S,5R)-menthol (Acros) were used as supplied. HN(SiMe3)2
(Aldrich), Ti(OiPr)4 (Aldrich), and TiCl4 (Aldrich) were distilled
before use. CpTi(OMe)3,[50] TiCl4(THF)2,[51] Ti(CH2Ph)4,[52]
MeN(CH2CH2OH)2 (2),[53] PhCH2N(CH2CH2OH)2 (3),[54]
MeN(CH2CH2OH)CH2CH(Ph)OH (4a) and MeN(CH2CH2OH)-
CH(Ph)CH2OH (4b) as a mixture 9:1,[34] MeN(CH2CH2OH)-
CH2CH(Me)OH (5),[55] and MeN(CH2CH2OH)CH2CH(Et)OH
(6)[55] were prepared according to the literature. 13C{1H} NMR
spectrum for 5: δ = 20.17 (Me), 42.42 (MeN), 59.21, 59.73 (2 NCH2
groups), 63.65, 65.52 (OCH2 and OCH groups) ppm. 13C{1H}
NMR spectrum for 6: δ = 9.86 (CH2CH3), 27.71 (CH2CH3), 42.48
(NCH3), 59.30, 59.75 (NCH2), 63.77, 68.91 (OCH and
[43]
OCH2) ppm. PhCH2N(CH2CH2OSiMe3)2
and MeN(CH2-
[38]
CH2OSn-nBu3)2
were prepared according to the method re-
ported previously. PhCH2N(CH2CH2OSiMe3)2: B.p. = 126–129 °C
(0.7 Torr). NMR spectra: 1H NMR: δ = 0.07 (s, 18 H, SiMe3), 2.67
(t, 4 H, NCH2), 3.61 (t, 4 H, OCH2), 3.69 (s, 4 H, PhCH2N), 7.18–
7.32 (m, 5 H, C6H5) ppm. 13C{1H} NMR: δ = –0.54 (SiMe3), 56.66
(NCH2), 60.07 (OCH2), 61.17 (PhCH2), 126.83, 128.13, 128.78,
139.83 (aromatic carbons) ppm. MeN(CH2CH2OSn-nBu3)2: NMR
spectra: 1H NMR: δ = 0.95–0.82 (m, 18 H, CH2CH3), 1.14–0.98
(m, 12 H, CH2CH3), 1.33–1.26 (m, 12 H, SnCH2CH2), 1.57–1.49
(m, 12 H, SnCH2), 2.24 (s, 3 H, NCH3), 2.47 (t, 4 H, NCH2), 3.74
(t, 4 H, OCH2) ppm. 13C{1H} NMR: δ = 13.61 (CH2CH3), 14.55
(CH2CH3), 27.16 (SnCH2CH2), 27.95 (SnCH2), 43.83 (NCH3),
62.65 (NCH2), 64.04 (OCH2) ppm.
All five-membered unsubstituted rings of the ocane skel-
etons in 19, 20, 23, 24, 25, and 27 adopt an “envelope”-like
conformation, all carbon atoms in the α positions to the N
atom occupy “flap” sites. In the case of substituted rings
their conformation may be treated as an “envelope” with α-
C atoms in “flap” sites (20, 23, and 25) or a “twist” (24 and
27).
A solution of n-butyllithium in hexane was obtained and analyzed
by the Gilman double-titration method.[56] CDCl3 was obtained
1
from Deutero GmbH and dried with P4O10. H NMR (300 MHz)
and 13C NMR (75 MHz) spectra were recorded with a Bruker–
Evance spectrometer (in CDCl3 at 295 K unless otherwise stated).
1
Chemical shifts in the H and 13C NMR spectra are given in ppm
relative to internal Me4Si. Elemental analyses were carried out by
the Microanalytical Laboratory of the Chemistry Department of
the Moscow State University.
Conclusion
We have found that tetraisopropoxytitanium or cyclo-
pentadienyltrimethoxytitanium react with one equivalent of
dialkanolamines 1–3 leading to the formation of the corre-
sponding dialkoxytitanocanes 13–16. The substitution reac-
tion of diisopropoxy derivative 15 with -(–)-menthol easily
occurs to give dimenthoxytitanocane 17. The nature of the
alkoxy substituent at the Ti atom strongly affects the struc-
ture and dynamic behavior of 13–17 in solution. The reac-
tion of Ti(OiPr)4 with two equivalents of dialkanolamines
1, 3–12 led to the corresponding spirobititanocanes 18–28
with a hexacoordinate Ti atom. The structure of latter com-
pounds is governed by the nature of the ligands: depending
on the substituents in the ocane skeleton the nitrogen atoms
occupy cis or trans positions around the Ti atom. Spirobitit-
anocane 18 is easily converted into the corresponding titan-
ocane 13 by its reaction with one equivalent of Ti(OiPr)4.
The reaction of titanocanes 14 and 15 with the different
dialkanolamines (1, 3 and 2, 8, respectively) did not give
the expected bisheteroleptic compounds but resulted in a
mixture of bishomoleptic titanocanes 18 and 29, 19 and 29
and 19 and 29, 19 and 24, respectively.
MeN(CH2CH2OH)CH2C(Ph)2OH (7): A mixture of N-methyl-
ethanolamine (1.15 g, 15 mmol) and 2,2-diphenyloxyrane (3.00 g,
15 mmol) was heated at 90 °C for 35 h. The resulting dense yellow
oil was crystallized from the mixture diethyl ether/hexane (1:1) at
–20 °C to give 7 as a white crystalline solid [3.14 g, 77%; 109–
110 °C (110–111 °C[46])]. NMR spectra: 1H NMR: δ = 2.12 (s, 3 H,
NCH3), 2.61 (t, 2 H, NCH2), 3.36 (s, 2 H, NCH2), 3.56 (t, 2 H,
OCH2), 7.16–7.20, 7.26–7.31, 7.46–7.49 (3 m, 10 H, 2 C6H5) ppm,
the signal from the OH groups was not observed. 13C{1H} NMR:
δ = 44.15 (NCH3), 59.86, 61.27, 67.76 (2 NCH2 and OCH2 groups),
75.60 [C(C6H5)2], 125.79, 126.73, 128.15, 146.55 (C6H5) ppm.
erythro-MeN(CH2CH2OH)CH(Ph)CH(Ph)OH (8): A mixture of
N-methylethanolamine (2.0 mL, 25 mmol) and trans-stilbene oxide
(4.91 g, 25 mmol) was heated at 130 °C for 22 h. The resulting
dense orange oil was crystallized from the mixture of diethyl ether/
hexane (1:1) at –20 °C to give 8 as a light yellow crystalline solid
1
(6.20 g, 91%; 90–91 °C). NMR spectra: H NMR: δ = 1.98 (br. s,
2 H, 2 OH), 2.13 (s, 3 H, NCH3), 2.38–2.51 (m, 2 H, NCH2), 3.30–
3.40 (m, 2 H, OCH2), 3.71 (d, 1 H, NCH), 5.22 (d, 1 H, OCH),
7.23–7.37 (m, 10 H, 2 C6H5) ppm. 13C{1H} NMR: δ = 37.36
(NCH3), 56.78 (NCH2), 57.97 (OCH2), 72.98 (NCH), 74.63 (OCH),
126.58, 127.89, 127.92, 128.30, 129.51, 134.85, 142.19 (C6H5).
1994
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Eur. J. Inorg. Chem. 2006, 1987–1999

Titanium Complexes of Dialkanolamine Ligands
FULL PAPER
C17H21NO2 (271.35): calcd. C 75.25, H 7.80, N 5.16; found C
75.33, H 7.82, N 5.32 ppm.
the elemental analyses were unobtainable because of the presence
of traces of 18.
MeN(CH2CH2O)2Ti(OiPr)2 (14): A mixture of alkanolamine 2
(2.14 g, 18.0 mmol), Ti(OiPr)4 (5.11 g, 18.0 mmol), and chloroform
(20 mL) was refluxed for 7 h, all volatiles were removed under re-
duced pressure. The residue was dissolved in hexane (20 mL), the
solution was filtered and stored at –30 °C for 18 h to give an oil
under a supernatant solution. The solvent was removed through a
cannula and 14 was obtained as a colorless oil (4.53 g, 89%). NMR
spectra: 1H NMR: δ = 1.07 (d, 12 H, CHCH3), 2.48 (s, 3 H, NCH3),
2.80 (br. s, 4 H, NCH2), 4.20 (br. s, 4 H, OCH2), 4.48 (br. s, 2 H,
OCH) ppm. 13C{1H} NMR: δ = 25.70 (CHCH3), 44.38 (NCH3),
59.50 (NCH2), 69.20 (OCH2), 76.30 (OCH) ppm. Satisfactory re-
sults for the elemental analyses were unobtainable because of the
presence of traces of 29.
threo-MeN(CH2CH2OH)CH(Ph)CH(Ph)OH (9): Analogously to
8, dialkanolamine 9 was obtained from N-methylethanolamine
(0.82 mL, 10 mmol) and cis-stilbene oxide (1.96 g, 10 mmol) as a
light yellow crystalline solid (2.26 g, 83%; 88–89 °C). NMR spec-
1
tra: H NMR: δ = 2.27 (s, 3 H, NCH3), 2.42–2.49 (m, 1 H), 2.69–
2.76 (m, 1 H) (NCH2), 3.65–3.78 (m, 2 H, OCH2), 3.69 (d, 1 H,
NCH), 5.05 (d, 1 H, OCH), 7.05–7.15, 7.18–7.23 (2 m, 10 H, 2
C6H5) ppm, the signal of OH groups was not observed. 13C{1H}
NMR: δ = 37.37 (NCH3), 55.39 (NCH2), 59.51 (OCH2), 71.49
(NCH), 75.24 (OCH), 127.33, 127.39, 127.68, 127.89, 127.92,
129.77, 133.36, 141.10 (C6H5) ppm. C17H21NO2 (271.35): calcd. C
75.25, H 7.80, N 5.16; found C 75.39, H 7.86, N 5.25.
MeN(CH2CH2OH)CH(C3H6)CHOH (10): A mixture of N-methyl-
ethanolamine (2.95 g, 40 mmol) and cyclopentene oxide (3.36 g,
40 mmol) was stirred at 85 °C for 20 h. The distillation of the reac-
tion mixture gave 10 as a viscous light-yellow liquid [5.29 g, 91%;
105–106 °C (0.2 Torr)]. NMR spectra: 1H NMR: δ = 1.93–1.35 (m,
6 H, cyclopentane 3CH2), 2.25 (s, 3 H, NCH3), 2.59 (m, 2 H,
NCH2), 2.74–2.81 (m, 1 H, NCH), 3.52–3.65 (m, 2 H, OCH2), 3.76
(br. s, 2 H, OH), 3.99–4.06 (m, 1 H, OCH) ppm. 13C{1H} NMR:
δ = 20.72, 24.39, 33.15 (cyclopentane carbons CH2), 38.64 (NCH3),
56.20 (NCH2), 58.57 (OCH2), 73.34 (NCH), 74.41 (OCH) ppm.
C8H17NO2 (159.23): calcd. C 60.35, H 10.76, N 8.80; found C
59.98, H 10.63, N 9.20.
PhCH2N(CH2CH2O)2Ti(OiPr)2 (15): The procedure was the same
as for 14 except that Ti(OiPr)4 (3.70 g, 13.0 mmol) was treated with
alkanolamine 3 (2.50 g, 13.0 mmol) in toluene. The compound 15
was obtained as a white oil (4.30 g, 92%). NMR spectra: 1H NMR:
δ = 1.26 (d, 12 H, CHCH3), 2.93 (br. s, 4 H, NCH2), 4.19 (s, 2 H,
PhCH2), 4.39 (br. s, 4 H, OCH2), 4.66 (br. s, 2 H, OCH), 7.23–7.34
(m, 5 H, C6H5) ppm. 13C{1H} NMR: δ = 26.11 (CHCH3), 54.21
(NCH2), 58.01 (PhCH2), 69.43 (OCH2), 76.53 (OCH), 128.01,
128.30, 131.01, 133.74 (C6H5) ppm. C17H29NO4Ti (359.28): calcd.
C 56.51, H 7.98, N 3.72; found C 56.83, H 8.14, N, 3.90.
Reaction of PhCH2N(CH2CH2OSiMe3)2 with TiCl4(THF)2:
PhCH2N(CH2CH2OSiMe3)2 (0.95 g, 2.8 mmol) was added drop-
wise to a suspension of TiCl4(THF)2 (0.94 g, 2.8 mmol) in toluene
(15 mL). The reaction mixture was refluxed for 14 h, and then fil-
tered off to give a yellow solid, which was insoluble in the usual
organic solvents. According to NMR spectroscopic data in (CD3)2-
SO, a mixture of unidentified compounds formed.
MeN(CH2CH2OH)CH(C4H8)CHOH (11): A mixture of N-methyl-
ethanolamine (13.2 mL, 0.165 mol) and cyclohexene oxide
(15.2 mL, 0.15 mol) was heated at 100 °C for 48 h. The distillation
of the reaction mixture gave 11 as a viscous colorless liquid
1
[22.89 g, 88%; 105–107 °C (0.2 Torr)]. NMR spectra: H NMR: δ
= 0.99–1.24, 1.59–1.69, 1.96–2.03 (3 m, 8 H, cyclohexane, 4 CH2),
2.19 (s, 3 H, NCH3), 2.14–2.22, 2.36–2.44, 2.58–2.67, 3.27–3.35,
3.48–3.59 (5 m, 6 H, NCH2, OCH2, NCH, OCH), 3.75 (br. s, 2 H,
2 OH) ppm. 13C{1H} NMR: δ = 21.82, 24.12, 25.20, 33.38 (cyclo-
hexane carbons CH2), 36.68 (NCH3), 54.98 (NCH2), 59.42
(OCH2), 69.25, 69.42 (NCH, OCH) ppm. C9H19NO2 (173.25):
calcd. C 62.39, H 11.05, N 8.08; found C 61.99, H 11.07, N 8.42.
Reaction of MeN(CH2CH2OSn-nBu3)2 with Cp2TiCl2: MeN(CH2-
CH2OSn-nBu3)2 (2.35 g, 3.4 mmol) was added dropwise to a solu-
tion of Cp2TiCl2 (0.60 g, 2.4 mmol) in CHCl3 (65 mL). The reac-
tion mixture was stirred for 10 h, then all volatiles were removed
under reduced pressure. According to NMR spectroscopic data of
the residue a mixture of CpSn-nBu3 with unidentified compounds
formed.
MeN(CH2CH2OH)CH(C6H4CH2)CHOH (12): Analogously to 8
(except only diethyl ether was used for recrystallization), dialkanol-
amine 12 was obtained from N-methylethanolamine (2.30 g,
30 mmol) and indene oxide (3.96 g, 30 mmol) as a light-yellow crys-
[PhCH2N(CH2CH2O)2Ti(OMe)2]2 (16): A solution of alkanol-
amine 3 (0.71 g, 3.6 mmol) in THF (10 mL) was added dropwise
at –50 °C to a solution of CpTi(OMe)3 (0.75 g, 3.6 mmol) in THF
(20 mL). The mixture was warmed to room temperature and stirred
overnight. The solid that formed was filtered off and recrystallized
from the mixture of dichloromethane/heptane (1:1) to give 16 as
white microcrystals (0.84 g, 77%). NMR spectra: 1H NMR: δ =
2.85–2.90, 3.05–3.10 (2 br. m, 4 H, NCH2), 4.17, 4.22 (2 s, 6 H,
OCH3), 4.43 (br. s, 2 H, PhCH2), 4.28–4.36, 4.57–4.63 (2 br. m, 4
H, OCH2), 7.25–7.36 (m, 5 H, C6H5) ppm. 13C{1H} NMR: δ =
54.22 (NCH2), 55.70 (PhCH2), 60.46, 64.74 (OCH3), 68.82 (OCH2),
127.88, 128.22, 131.47, 134.01 (C6H5) ppm. Satisfactory results for
the elemental analyses were unobtainable because of the presence
of traces of 19.
1
talline solid (5.82 g, 94%; 75–76 °C). NMR spectra: H NMR: δ =
2.44 (s, 3 H, NCH3), 2.82–2.95, 3.26–3.34 [2 m, 2 H, CH2C(OH)
H], 2.88–2.95 (m, 2 H, NCH2), 3.19 (br. s, 2 H, 2 OH), 3.66–3.79
(m, 2 H, OCH2), 4.29 (d, 1 H, NCH), 4.66 (q, 1 H, OCH), 7.23–
7.35 (m, 4 H, aromatic protons) ppm. 13C{1H} NMR: δ = 37.34
(CHCH2), 39.68 (NCH3), 55.87 (NCH2), 58.44 (NCH), 73.75
(OCH2), 113.46 (OCH), 125.06, 125.08, 126.79, 127.94, 140.00,
140.10 (aromatic carbons) ppm.
PhN(CH2CH2O)2Ti(OiPr)2 (13): A mixture of alkanolamine 1
(2.00 g, 11.0 mmol), Ti(OiPr)4 (3.14 g, 11.0 mmol), and chloroform
(20 mL) was refluxed for 8 h, and all volatiles were removed under
reduced pressure. Hexane (20 mL) was added to a yellow, waxy
solid. The solution was filtered and the solvent removed under re-
duced pressure to give 13 as a yellow solid (3.05 g, 80%). NMR
PhCH2N(CH2CH2O)2Ti(OMenth)2 (17): -(–)-Menthol (1.56 g,
10 mmol) was added to a stirred solution of the compound 15
(1.80 g, 5.0 mmol) in chloroform (30 mL) at room temperature. The
spectra: 1H NMR: δ = 1.19 (br. s, 12 H, CH3), 3.47 (br. s, 4 H, reaction mixture was refluxed for 6 h, all volatiles were removed
NCH2), 4.30–4.90 (br. m, 6 H, OCH2, OCH), 6.53–6.70, 7.07–7.19
under reduced pressure. Hexane (20 mL) was added to the white
(2 m, 5 H, C6H5) ppm. 13C{1H} NMR (323 K): δ = 26.24 (CH3), oil. The mixture was stored at –30 °C for several days. The solid
55.21 (broad, NCH2), 73.22 (broad, OCH2), 77.44 (OCH), 113.38, that formed was filtered off to give 17 as a white powder (2.64 g,
1
116.58, 130.05, 149.41 (broad, C6H5) ppm. Satisfactory results for
96%). NMR spectra: H NMR: δ = 0.76 (d, 3 H, CH3), 0.82 (br.
Eur. J. Inorg. Chem. 2006, 1987–1999
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1995

S. S. Karlov et al.
FULL PAPER
d, 6 H, CH3), 0.85–0.95 (m, 13 H, CH3, CH2), 1.01–1.18 (m, 4 H, 18.0 mmol) and Ti(OiPr)4 (2.56 g, 9.0 mmol) was refluxed for 15 h
CH2), 1.38 (br. s, 2 H, CH), 1.50–1.62 (br. m, 4 H, CH2), 2.07– in toluene (15 mL). The compound 21 was obtained as a colorless
2.12, 2.17–2.22 (2 br. m, 2 H, CH), 2.33–2.48 (br. m, 2 H, CH),
oil (2.67 g, 96%), a mixture of diastereomers. NMR spectra: 1H
2.84, 3.00 (2 br. s, 4 H, NCH2), 3.83–3.90, 4.05–4.14 (2 m, 2 H, NMR: δ = 1.00, 1.02, 1.11 (3 d, 6 H, CHCH3), 2.41, 2.43, 2.45 (3
OCH), 4.16 (br. s, 2 H, PhCH2), 4.33, 4.46 (2 br. s, 4 H, OCH2), s, 6 H, NCH3), 2.48–2.53, 2.60–2.81, 3.00–3.24 (3 br. m, 8 H,
7.26–7.37 (m, 5 H, C6H5) ppm. 13C{1H} NMR: δ = 15.78, 21.20,
NCH2), 4.00–4.09, 4.46–4.51 (2 m, 4 H, OCH2), 4.70 (br. s, 2 H,
22.25 (CH3), 22.70 (CH2), 25.45, 31.65 (CH), 34.63, 46.51 (CH2), OCH) ppm. 13C{1H} NMR (323 K): δ = 20.90, 21.05, 21.22
50.98 (CH), 54.22 (broad, NCH2), 57.84 (PhCH2), 69.37 (OCH2), (CHCH3), 43.42, 44.27, 44.51 (NCH3), 58.92, 59.70, 59.91 (NCH2),
84.14, 85.01 (OCH), 128.05, 128.36, 131.10, 133.89 (C6H5) ppm. 69.57, 69.51 (OCH2), 74.89, 75.04 (OCH) ppm, the signals of se-
Satisfactory results for the elemental analyses were unobtainable
because of the presence of traces of 19.
veral carbons were not found. C12H26N2O4Ti (310.21): calcd. C
46.46, H 8.45, N 9.03; found C 46.20, H 8.56, N 8.94.
[MeN(CH2CH2O)(CH2CHEtO)]2Ti (22): The procedure was the
same as for 18 except that alkanolamine 6 (2.97 g, 20 mmol) was
treated with Ti(OiPr)4 (2.87 g, 10 mmol) in toluene (15 mL). Com-
pound 22 was obtained as a colorless oil (3.18 g, 94%), a mixture
of diastereomers. NMR spectra: 1H, δ = 0.78–0.81 (m, 6 H,
CH2CH3), 1.30 (br. s, 4 H, CH2CH3), 2.42 (br. s, 6 H, NCH3),
2.45–2.55, 2.76–2.85, 3.15–3.39 (3 br. m, 8 H, NCH2), 4.07, 4.48 (2
br. s, 6 H, OCH2, OCH); 13C{1H}, δ = 9.08 (broad, CH2CH3),
27.67 (broad, CH2CH3), 41.93, 43.71 (NCH3), 59.22, 60.35
(NCH2), 68.25 (broad, OCH2), 79.64 (broad, OCH), the signals of
several carbons were not found. C14H30N2O4Ti (338.27): calcd. C
49.71, H 8.94, N 8.28; found C 49.29, H 8.73, N 8.09.
[PhN(CH2CH2O)2]2Ti (18): A mixture of alkanolamine 1 (0.83 g,
4.6 mmol), Ti(OiPr)4 (0.65 g, 2.3 mmol), and toluene (15 mL) was
refluxed for 13 h, and all volatiles were removed under reduced
pressure. The residue was recrystallized from toluene to give 18 as
a yellow solid (0.77 g, 82%). NMR spectra: 1H NMR: δ = 3.41 (br.
s, 8 H, NCH2), 4.17 (br. s, 8 H, OCH2), 6.58–6.70, 7.13–7.26 (m,
10 H, C6H5) ppm 13C{1H} NMR: δ = 56.71 (broad, NCH2), 73.52
(broad, OCH2), 112.01, 116.02, 130.46, 148.16 (C6H5) ppm.
C20H26N2O4Ti (406.30): calcd. C 59.12, H 6.45, Ti 11.79; found C
59.46, H 6.44, Ti 11.51.
[PhCH2N(CH2CH2O)2]2Ti (19). Method 1: The procedure was the
same as that for 18 except that Ti(OiPr)4 (0.94 g, 3.3 mmol) was
treated with alkanolamine 3 (1.29 g, 6.6 mmol). The compound
was obtained as white microcrystals (1.22 g, 85%). NMR spectra:
1H NMR: δ = 3.00 (t, 8 H, NCH2), 4.11 (s, 4 H, PhCH2), 4.49 (t,
8 H, OCH2), 7.27–7.38 (m, 10 H, C6H5) ppm. 13C{1H} NMR: δ =
53.48 (broad, NCH2), 56.73 (PhCH2), 70.22 (OCH2), 127.92,
128.29, 130.99, 133.90 (C6H5) ppm. C22H30N2O4Ti (434.38): calcd.
C 60.83, H 6.96, N 6.45; found C 61.01, H 7.10, N 6.59.
[MeN(CH2CH2O)(CH2CPh2O)]2Ti (23). Method 1: The procedure
was the same as for 18 except that alkanolamine 7 (0.97 g,
3.6 mmol) was treated with Ti(OiPr)4 (0.51 g, 1.8 mmol) in chloro-
form (10 mL). Compound 23 was obtained as white microcrystals
(0.70 g, 90%). NMR spectra: 1H NMR: δ = 2.42 (br. s, 6 H,
NCH3), 2.84, 2.97 (2 br. s, 4 H, NCH2), 3.85, 3.98 (2 d, 4 H,
NCH2CPh2), 4.35 (br. s, 4 H, OCH2), 7.10–7.30, 7.50–7.56 (2 m,
20 H, C6H5) ppm. 13C{1H} NMR: δ = 44.79 (NCH3), 61.45
(NCH2), 70.41 (OCH2), 88.75 (OCPh2), 125.46, 125.51, 126.08,
126.14, 127.98, 128.01, 149.68 (C6H5) ppm, the signals of several
carbons were not found. C34H38N2O4Ti (586.54): calcd. C 69.62,
H 6.53, Ti 8.16; found C 69.86, H 6.64, Ti 8.17.
Method 2: A solution of alkanolamine 3 (1.10 g, 5.6 mmol) and
triethylamine (1.15 g, 11.4 mmol) in THF (30 mL) was added drop-
wise at –50 °C to a suspension of TiCl4(THF)2 (0.94 g, 2.8 mmol)
in THF (20 mL). The mixture was stirred for 1 h at the same tem-
perature, and was then warmed to room temperature overnight. All
volatiles were evaporated under reduced pressure. A white solid was
extracted with hot benzene (3×20 mL). The solvent was removed
under reduced pressure, and the residue was recrystallized from
toluene to give 19 as white microcrystals (0.4 g, 33%).
Method 2: Alkanolamine 7 (1.14 g,4.2 mmol) was added to a solu-
tion of titanium tetrabenzyl (0.87 g, 2.1 mmol) in toluene (50 mL)
at (–40 °C). The reaction mixture was slowly warmed to room tem-
perature and then refluxed for 1 h. The resulting colorless solution
was concentrated under vacuum, to give 23 as a white solid (1.23 g,
100%). Crystals, suitable for X-ray analysis, were obtained by
recrystallization from the mixture of dichloromethane/n-hexane.
Method 3: A solution of alkanolamine 3 (0.70 g, 3.6 mmol) in tolu-
ene (5 mL) was added dropwise to a solution of Ti(CH2Ph)4
(0.75 g, 1.8 mmol) in toluene (40 mL) at (–40 °C). The reaction
mixture was slowly warmed to room temperature and then refluxed
for 1 h. The resulting solution was concentrated under vacuum, to
give 20 as a white solid (0.78 g, 100%).
erythro-[MeN(CH2CH2O)(CHPhCHPhO)]2Ti (24): The procedure
was the same as that for 13 except that alkanolamine 8 (2.17 g,
8.0 mmol) was treated with Ti(OiPr)4 (1.14 g, 4.0 mmol) in chloro-
form (20 mL). Compound 24 was obtained as colorless microcrys-
tals (1.97 g, 84%), a mixture of diastereomers. NMR spectra: 1H
NMR: δ = 2.57 (br. s, 6 H, NCH3), 2.96–3.38 (br. m, 4 H, NCH2),
4.15–4.32 (br. m, 4 H, OCH2), 4.50–4.59 (br. m, 2 H, NCH), 6.10–
6.15, 6.26–6.45 (br. m, 2 H, OCH), 7.05–7.34 (m, 20 H, C6H5) ppm.
13C{1H} NMR: δ = 42.29, 42.36, 45.82 (NCH3), 60.63 (broad,
NCH2), 69.72, 70.46 71.48, 71.52 (OCH2, NCHPh), 86.51 (broad,
OCHPh), 125.90, 126.22, 126.43, 126.90, 127.11, 127.27, 127.45,
127.68, 127.84, 131.21, 142.11, 142.77 (C6H5) ppm, the signals of
several carbons were not found. C34H38N2O4Ti (586.54): calcd. C
69.62, H 6.53, Ti 8.16; found C 70.55, H 6.83, N 4.55.
[MeN(CH2CH2O)(CH2CHPhO)]2Ti (20): The procedure was the
same as that for 18 except that Ti(OiPr)4 (0.77 g, 2.7 mmol) was
treated with a mixture of (4a and 4b) (9:1) (1.05 g, 5.4 mmol). The
compound 20 was obtained as colorless microcrystals, a mixture of
diastereomers. NMR spectra: 1H NMR: δ = 2.61, 2.64, 2.66 (3 s, 6
H, NCH3), 2.72–2.85, 2.98–3.25, 3.37–3.54 (3 m, 8 H, NCH2),
4.26–4.31, 4.57–4.66 (2 m, 4 H, OCH2), 5.63–5.70, 5.75–5.81 (2 m,
2 H, OCH), 7.13–7.47 (m, 10 H, C6H5) ppm. 13C{1H} NMR: δ =
42.15, 42.72, 44.18 (NCH3), 56.23, 59.49 (NCH2), 69.43 (broad,
OCH2), 80.67, 80.78 (OCH), 124.33, 124.86, 125.55, 126.18, 126.35,
126.93, 127.32, 128.04, 128.24, 143.73, 143.85, 144.18 (C6H5) ppm,
the signals of several carbons were not found, the signals of sol-
vated toluene are not described. C22H30N2O4Ti*PhCH3 (526.51):
calcd. C 66.16, H 7.27, N 5.32; found C 66.06, H 7.01, N 4.89.
threo-[MeN(CH2CH2O)(CHPhCHPhO)]2Ti (25): The procedure
was the same as that for 13 except that the mixture of alkanolamine
9 (2.00 g, 7.4 mmol),Ti(OiPr)4 (1.05 g, 3.7 mmol) and chloroform
(20 mL) was refluxed for 16 h. The compound 25 was recrystallized
[MeN(CH2CH2O)(CH2CHMeO)]2Ti (21): The procedure was the from the mixture of dichloromethane/heptane (4:1) and isolated as
same as for 18 except that the mixture of alkanolamine 5 (2.40 g, colorless microcrystals (1.52 g, 96%), a mixture of diastereomers.
1996
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1987–1999

Titanium Complexes of Dialkanolamine Ligands
FULL PAPER
NMR spectra: 1H NMR: δ = 2.42, 2.47, 2.55 (s, 6 H, NCH3), 2.68–
2.79, 3.35–3.48, 3.93–4.05 (m, 4 H, NCH2), 4.26–4.32, 4.41–4.48
1.07–1.15, 1.61–1.68, 1.85–1.91 (br. m, 16 H, cyclopentane 8 CH2),
2.41 (br. s, 6 H, NCH3), 2.25–2.37, 2.60–2.90, 3.10–3.14, 3.29–3.36
(m, 2 H, NCH), 4.50–4.58, 4.92–4.97 (m, 4 H, OCH2), 5.94–6.02 (br. m, 6 H, NCH, NCH2), 3.91–4.13, 4.29–4.37 (br. m, 4 H,
(m, 2 H, OCH), 7.00–7.42 (m, 20 H, C6H5) ppm. 13C{1H} NMR:
δ = 38.40, 39.87, 40.20 (NCH3), 54.10, 56.84 (NCH2), 69.80, 70.00,
OCH2), 4.41–4.63 (br. m, 2 H, OCH); 13C{1H}, δ = 23.14, 24.57,
24.88, 34.95 (broad, CH2 groups of cyclohexane ring), 39.61
73.09 (NCHPh), 78.84, 79.36 (OCH2), 84.93, 86.01 (OCH), 126.86, (NCH3), 52.38 (NCH2), 70.34, 73.00 (NCH, OCH2), 82.90 (broad,
127.08, 127.37, 127.54, 127.84, 128.14, 128.38, 130.15, 131.01, OCH), the signals of several carbons were not found.
131.75, 133.36, 143.45 (C6H5) ppm, the signals of several carbons C18H34N2O4Ti (390.37): calcd. C 55.39, H 8.78, N 7.19; found C
were not found, the signals of solvated dichloromethane are not
described. C34H38N2O4Ti·CH2Cl2 (671.49): calcd. C 62.60, H 6.00,
N 4.17; found C 62.08, H 5.84, N 3.85.
55.65, H 8.76, N 7.21.
{MeN(CH2CH2O)[CH(C6H4CH2)CHO]}2Ti (28): The procedure
was the same as that for 18 except that alkanolamine 12 (1.00 g,
4.8 mmol) was treated with Ti(OiPr)4 (0.69 g, 2.4 mmol) in toluene
(15 mL). The compound 28 was recrystallized from the mixture of
toluene/heptane (2:1) and isolated as a yellow solid (0.91 g, 83%),
a mixture of diastereomers. NMR spectra: 1H (323 K), δ = 2.71
(br. s, 6 H, NCH3), 2.60–2.66, 2.92–3.04 (m, CH2), 3.15, 3.28 (br.
s, 4 H, NCH2), 4.25–4.34 (m, 4 H, OCH2), 4.64 (br. s, 2 H, NCH),
5.13 (br. s, 2 H, OCH), 7.09–7.28 (m, 8 H, C6H4); 13C{1H} (323 K),
δ = 37.85 (broad, NCH3, CH2), 57.88 (broad, NCH2), 69.09 (broad,
OCH2), 76.31 (broad, NCH), 83.62 (broad, OCH) 123.82, 125.44,
126.22, 127.20, 139.37, 140.39 (C6H4). C24H30N2O4Ti (458.37):
calcd. C 62.89, H 6.60, N 6.11; found C 62.43, H 6.32, N 5.94.
{MeN(CH2CH2O)[CH(CH2)3CHO]}2Ti (26): The procedure was
the same as that for 18 except that the mixture of alkanolamine 10
(1.08 g, 6.8 mmol), Ti(OiPr)4 (0.97 g, 3.4 mmol) and toluene (7 mL)
was refluxed for 15 h. The compound 26 was obtained as a yellow
1
solid (1.10 g, 89%), a mixture of diastereomers. NMR spectra: H
NMR: δ = 1.21–1.36, 1.55–1.79 (br. m, 12 H, cyclopentane 6 CH2),
2.46, 2.49, 2.50 (c, 6 H, NCH3), 2.41–2.46, 3.01–3.15 (br. s, 6 H,
NCH2, NCH), 4.04–4.08, 4.65–4.72 (m, 4 H, OCH2), 4.73–4.81 (m,
2 H, OCH) ppm 13C{1H} NMR: δ = 16.20, 18.56, 27.34 (broad,
CH2 groups of cyclopentane rings), 40.61, 41.20, 41.53 (NCH3),
53.59, 53.88 (NCH2), 71.02, 71.17, 71.38 (OCH2), 73.50 (broad,
NCH), 84.28 (broad, OCH) ppm, the signals of several carbons
were not found. C16H30N2O4Ti (362.29): calcd. C 53.04, H 8.35, N
7.73; found C 52.12, H 8.11, N 7.53.
Reaction of 14 with Alkanolamine 1: Alkanolamine 1 (0.83 g,
4.6 mmol) was added to a solution of 14 (1.30 g, 4.6 mmol) in tolu-
ene (10 mL). The mixture was refluxed for 2 h, and all volatiles
were removed under reduced pressure. According to NMR spectro-
scopic data a mixture of 18 and 29[20] was formed.
{MeN(CH2CH2O)[CH(CH2)4CHO]}2Ti (27): The procedure was
the same as that for 18 except that alkanolamine 11 (1.49 g,
8.6 mmol) was treated with Ti(OiPr)4 (1.22 g, 4.3 mmol) in toluene
(15 mL). Compound 27 was obtained as colorless microcrystals
Reaction of 14 with Alkanolamine 3: Alkanolamine 3 (0.90 g,
4.6 mmol) was added to a solution of 14 (1.30 g, 4.6 mmol) in tolu-
1
(1.54 g, 92%), a mixture of diastereomers. NMR spectra: H, δ =
Table 4. Crystal data, data collection, structure solution, and refinement parameters for 16, 19, 20, 23, 24, 25, and 27.
16 19 20 23 24 25
C26H38N2O8Ti2· C22H30N2O4Ti C22H30N2O4Ti· C34H38N2O4Ti· C34H38N2O4Ti· C34H38N2O4Ti· C18H34N2O4Ti
27
Formula
2CH2Cl2
772.24
orthorhombic
Pbcn
15.9481(9)
9.8954(5)
22.2450(12)
C7H8
526.51
monoclinic
P21/c
12.8626(12)
16.5027(16)
12.5842(13)
90.558(2)
2671.1(5)
4
2CH2Cl2
756.42
monoclinic
C2/c
21.447(3)
8.223(1)
21.056(3)
98.54(1)
3672.2(9)
4
0.5C7H8
632.63
monoclinic
P21/c
13.401(1)
12.780(2)
19.660(3)
91.28(1)
3366.2(8)
4
CH2Cl2
671.49
Mr [g·mol–1
Crystal system
Space group
a [Å]
b [Å]
c [Å]
]
434.38
monoclinic
P2/n
9.443(4)
12.749(3)
18.207(3)
93.17(2)
2188.6(11)
4
390.37
monoclinic
C2/c
21.545(5)
8.943(4)
10.435(6)
93.79(4)
2006.2(15)
4
orthorhombic
Pbcn
6.9964(4)
20.5113(11)
23.6918(14)
β [º]
V [Å3]
Z
3510.5(3)
4
1.461
0.807
1600
3399.9(3)
4
1.312
0.449
1408
dcalcd [g·cm–3
]
1.318
0.421
920
1.309
1.357
1120
1.368
0.564
1576
1.248
0.295
1340
1.292
0.450
840
Abs. coeff. [mm–1
F(000)
]
Diffractometer
Temperature [K]
θ range [º]
Bruker SMART Nonius CAD4 Bruker SMART Stoe IPDS II
Nonius CAD4 Bruker SMART Nonius CAD4
120
293
120
173
293
120
293
3.04–28.00
–15 Յ h Յ 21
–13 Յ k Յ 8
–29 Յ l Յ 29
16611
2.24–25.48
–11 Յ h Յ 11 –14 Յ h Յ 16
–3 Յ k Յ 15
–4 Յ l Յ 22
6766
1.23–28.00
1.92–25.98
2.07–25.47
1.72–28.00
2.47–25.97
–26 Յ h Յ 26
–4 Յ k Յ 11
–4 Յ l Յ 12
4419
Index ranges
–26 Յ h Յ 26 –16 Յ h Յ 16 –9 Յ h Յ 9
–21 Յ k Յ 21
–15 Յ l Յ 16
17996
–10 Յ k Յ 9
–25 Յ l Յ 25
24987
–2 Յ k Յ 15
–3 Յ l Յ 23
9029
–27 Յ k Յ 15
–31 Յ l Յ 29
21508
Reflections
collected
Independent
reflections
Rint
4205
4071
6400
3570
6247
4120
1969
0.03332
4205/283
1.051
0.0399
0.1088
0.0283
4071/281
1.008
0.0372
0.1094
0.0401
6400/478
1.027
0.0507
0.1352
0.0746
3570/215
0.787
0.0323
0.0619
0.0306
6247/390
1.007
0.0446
0.1498
0.0394
4120/281
1.090
0.0536
0.1315
0.1158
1969/115
0.991
0.0637
0.1788
Data/param.
GOF on F2
R1 [I Ͼ 2σ(I)]
wR2 (all data)
Largest diff.
0.875/–0.312
0.226/–0.238
0.403/–0.476
0.265/–0.379
0.691/–0.399
1.318/–1.085
1.059/–0.589
peak/hole [e·Å–3
]
Eur. J. Inorg. Chem. 2006, 1987–1999
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1997

S. S. Karlov et al.
FULL PAPER
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ene (10 mL). The mixture was refluxed for 2 h, and all volatiles
were removed under reduced pressure. According to NMR spectro-
scopic data, a mixture of 19 and 29[20] was formed.
Reaction of 15 with Alkanolamine 2: Alkanolamine 2 (0.46 g,
2.5 mmol) was added to a solution of 15 (0.91 g, 2.5 mmol) in chlo-
roform (15 mL). The mixture was refluxed for 3 h, and all volatiles
were removed under reduced pressure. According to NMR spectro-
scopic data, a mixture of 19 and 29[20] was formed.
Reaction of 15 with Alkanolamine 8: Alkanolamine 8 (1.32 g,
4.9 mmol) was added to a solution of compound 15 (1.75 g,
4.9 mmol) in toluene (10 mL). The mixture was refluxed for 2 h,
and all volatiles were removed under reduced pressure. Ether
(20 mL) was added to the residue, the precipitate was filtered off
to give 19 as a white powder (1.02 g). According to NMR spectro-
scopic data, the mother liquor contained a mixture of 19 and 24.
[9]
[10]
[11]
[12]
[13]
[14]
[15]
Reaction of 18 with Ti(OiPr)4: Ti(OiPr)4 (0.52 g, 1.8 mmol) was
added dropwise to a solution of compound 18 (0.74 g, 1.8 mmol)
in chloroform (20 mL), and the reaction mixture was refluxed for
5 h. After cooling to room temperature, all volatiles were removed
under reduced pressure. Hexane (10 mL) was added to the yellow
oil. The solution was filtered, and the solvent was removed under
reduced pressure to give 13 as a yellow solid (1.22 g, 97%).
Reaction of 19 with TiCl4: TiCl4 (0.44 g, 2.3 mmol) was added at
–78 °C to a suspension of 19 (1.00 g, 2.3 mmol) in toluene (15 mL)
and the mixture was stirred for 2 h at the same temperature. A
yellow solid formed. The reaction mixture was warmed to room
temperature, and all volatiles were removed under reduced pressure.
The formed yellow solid was insoluble in the usual organic solvents.
According to NMR spectroscopic data in (CD3)2SO, a mixture of
unidentified compounds formed.
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
X-ray Crystallographic Study: Crystal data, data collection, struc-
ture solution, and refinement parameters for compounds 16, 19,
20, 23, 24, 25, and 27 are given in Table 4. Experimental data were
collected using Mo-Kα radiation (λ = 0.71073 Å). The structures
were solved by direct methods[57] and refined by full-matrix least-
squares based on F2 with anisotropic thermal parameters for all
non-hydrogen atoms.[58] In the structures 16, 20, and 25, all hydro-
gen atoms were found from diff. Fourier syntheses and refined iso-
tropically. As for 19, 23, 24, and 27 all hydrogen atoms were placed
in calculated positions and refined using a riding model. The struc-
ture 25 contains disordered CH2Cl2 molecules lying on a crystallo-
graphic twofold axis; 24 contains disordered toluene molecules ly-
ing on a crystallographic inversion center. In 19, one of the two
independent molecules possesses disordered -CH2CH2- skeleton
fragments with an occupancy ratio of 0.71/0.29.
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
CCDC-292591 to -292597 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
S. Fokken, T. Spaniol, H.-C. Kang, W. Massa, J. Okuda, Orga-
nometallics 1996, 15, 5069–5072.
Acknowledgments
L. Lavant, T.-I. Chou, Y. Chi, C. W. Lehmann, L. Toupet, J.-
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A. V. C. is grateful to the Russian Science Support Foundation.
This work was supported by the Philipps-University Marburg,
Chemistry Department, with a grant for K. V. Z., as well as RFBR
under grant 06-03-33032-a.
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Received: December 29, 2005
Published Online: March 23, 2006
Eur. J. Inorg. Chem. 2006, 1987–1999
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1999