Co-ordinative ability of the new compounds [Ti(η5-C5H4R)2-(C≡CBu t)2] (R = PPh2, Ph2P=O or Ph2P=S) as precursors in the synthesis of heterodi- And heterotri

Article abstract of DOI:10.1039/a807905f

full title:Co-ordinative ability of the new compounds [Ti(η⁵-C₅H₄R)₂-(C≡CBu ^t)₂] (R = PPh₂, Ph₂P=O or Ph₂P=S) as precursors in the synthesis of heterodi- An

Full text of DOI:10.1039/a807905f

View Article Online / Journal Homepage / Table of Contents for this issue
Co-ordinative ability of the new compounds [Ti(ç5-C5H4R)2-
t
᎐
(C᎐CBu ) ] (R ؍ PPh , Ph P᎐O or Ph P᎐S) as precursors in
᎐
᎐
᎐
2
2
2
2
the synthesis of heterodi- and heterotri-nuclear species. Crystal
5
2
t
᎐
structure of [ClCu(ì-ç :êP-C H PPh ) Ti(ì-ç -C᎐CBu ) CuCl]
᎐
5
4
2 2
2
Esther Delgado,*,a Elisa Hernández,a Noelia Mansilla,a M. Teresa Morenob and Michal Sabatc
a Departamento de Química Inorgánica, Facultad de Ciencias, Universidad Autónoma de
Madrid, 28249 Madrid, Spain. E-mail: esther.delgado@uam.es
b Departamento de Química, Universidad de la Rioja, 26001 Logroño, Spain
c Department of Chemistry, University of Virginia, VA 22901, Charlottesville, USA
Received 12th October 1998, Accepted 23rd December 1998
5
t
᎐
New mononuclear bis(alkyne) derivatives of functionalised titanocene [Ti(η -C H R) (C᎐CBu ) ] (R = PPh 1,
᎐
5
4
2
2
2
Ph P᎐O 7 or Ph P᎐S 8) have been isolated by reaction of [Ti(η5-C H R) Cl ] (R = PPh Ph P᎐O or Ph P᎐S)
and LiC᎐CBu in diethyl ether. The reactions of the former species with (CuCl) and [Mo(CO) (nbd)] have been
investigated. Novel heterobi- [L M(µ-η :κP-C H PPh ) Ti(µ-η -C᎐CBu ) ] [ML = CuCl 4 or Mo(CO) 5],
[{η -C H P(E)Ph } Ti(µ-η -C᎐CBu ) CuCl] (E = O 9 or S 10) and heterotri-nuclear complexes [L M(µ-η :κP-
᎐
᎐
᎐
᎐
2
2
2
5
4
2
2
2,
2
t
᎐
᎐
n
4
5
2
t
᎐
᎐
n
5
4
2
2
2
n
4
5
2
t
5
᎐
᎐
5
4
2
2
2
n
2
t
᎐
C H PPh ) Ti(µ-η -C᎐CBu ) CuCl] [ML = CuCl 2 or Mo(CO) 6] have been synthesized. The crystal structure
᎐
5
4
2
2
2
n
4
of compound 2 has been solved.
PPh , Ph P᎐O or Ph P᎐S) and their reactions as precursors of
Introduction
᎐
᎐
2
2
2
heterodi- and heterotri-nuclear species. The crystal structure
5
2
t
In the last years our group has focussed its interest on the syn-
thesis of thiolate derivatives of functionalised titanocenes and
their further use as precursors of new early–late heterometallic
compounds [(η5-C5H4RЈ)2Ti(µ-SR)2M(C6F5)2] (RЈ = H or
SiMe3; R = Ph or C6F5),1 [(OC)4Mo(µ-η5 :κP-C5H4PPh2)2-
Ti(µ-SPh)2M(C6F5)2] (M = Pd or Pt),2 [(C6F5)2Pt(µ-η5 :κP-
᎐
of [ClCu(µ-η :κP-C H PPh ) Ti(µ-η -C᎐CBu ) CuCl] has been
᎐
5
4
2
2
2
determined by a X-ray diffraction study.
Results and discussion
Treatment of [Ti(η5-C5H4PPh2)2Cl2] with 2 equivalents of
5
t
t
C5H4PPh2)2Ti(SPh)2]3
and
᎐
[(η -C H SiMe )(SC᎐CBu )Ti-
᎐
5 4 3
4
LiC᎐CBu in diethyl ether at Ϫ20 ЊC affords the compound
᎐
᎐
᎐
5
t
5
t
᎐
᎐
(µ-η :κP-C H PPh )(µ-SC᎐CBu )M(C F ) ] (M = Pd or Pt).
[Ti(η -C H PPh ) (C᎐CBu ) ] 1 in high yield. Complex 1 is
᎐
5
4
2
6
5
2
5 4 2 2 2
Different co-ordination situations, such as P,P; S,S or P,S,
have been observed in these species. The chemistry of transition
metal acetylides is a subject of growing interest in part due
stable in the solid state but decomposes gradually in solution
under an inert atmosphere. The 31P-{1H} NMR spectrum
exhibits a signal (δ Ϫ15.1) in the same range to that observed
for [Ti(η5-C5H4PPh2)2Cl2]14 and [Ti(η5-C5H4PPh2)2(SPh)2].3 The
two resonances that appear in the 13C-{1H} NMR spectrum at
δ 138.2 and 115.8, as well as a band at 2069 cmϪ1 in the IR, are
consistent with the presence of two equivalent alkyne groups
5
᎐
to the versatility of C᎐CR groups as bridging ligands. In
᎐
particular for titanocene acetylides, whereas complexes [(η5-
6
5
᎐
C H ) Ti(C᎐CPh) Pt(PR )] (R = Ph or C H ) and [(η -C H ) -
᎐
5
5
᎐
2
2
3
6
11
5
5 2
t
7
Ti(C᎐CBu ) Pt(C F ) ] show a symmetrical double bridge
᎐
2
6
5 2
µ-η2 or µ-η1 alkyne, the compound [(η -C H ) Ti(C᎐CBu ) -
σ co-ordinated to the titanium atom. The H NMR spectrum
5
t
1
᎐
᎐
5
5
2
2
Pt(PPh3)]8 exhibits asymmetric µ-η2 and µ-η1 bridges.
in the Cp region shows two signals at δ 6.24 and 6.12 corre-
sponding to the four protons of each ring and a singlet at δ 1.14
assigned to the But group. The lower electronegativity of
Although chelating bis(alkynyl) systems (µ-η2) can be in-
plane (tweezer) or out-of plane (V-shape) bonded to the other
metal, data reported on bis(alkynyl) titanocenes reveal that
the metal centre M is located in the plane of the 3-titanium-
1,4-diyne ligand. Lang and co-workers have carried out inter-
esting studies in this field by using functionalised titanocenes as
metalloligands to prepare some heterometallic species showing
t
᎐
C᎐CBu compared to that of the chloride ligand is responsible
᎐
for the shifting of the Cp resonances upfield.
The chemistry of CuI with phosphines is quite well known,
particularly that related to monophosphines.15 On the other
hand, in the last few years several papers have been reported
concerning the co-ordination of CuX moieties through
5
᎐
a tweezer-like interaction, [(η -C H SiMe ) Ti(C᎐CSiMe ) -
᎐
5
4
3
2
3 2
MR] (M = Cu or Ag; R = alkyl or aryl),9 [(η5-C5H4-
C᎐CR groups of some alkynyl derivatives of titanocenes.
16
᎐
᎐
SiMe ) Ti(C᎐CSiMe ) MCl ] (M = Fe, Co or Ni) and [(η5-
Taking into account these precedents and due to the possibility
10
᎐
᎐
3
2
3
2
2
5
t
᎐
᎐
C H SiMe ) Ti(C᎐CSiMe ) MX] (M = Cu or Ag; X = halide
for [Ti(η -C H PPh ) (C᎐CBu ) ] 1 to act as a Lewis base
᎐
᎐
5
4
3
2
3
2
5
4
2
2
2
or pseudohalide).11 In addition, extended Hückel calculations
carried out by these authors on some of the above mentioned
complexes justify this type of interaction.9,11
through the PPh and C᎐CBu groups, in order to know its
t
᎐
᎐
2
co-ordinative preferences we carried out the reaction between
complex 1 and CuCl in 1:1 stoichiometry, which gave the
5
2
᎐
On the other hand, the co-ordination chemistry of phosphine
oxides and sulfides has been a subject of study,12 however data
reported on related phosphoryl- and thiophosphoryl-cyclo-
pentadienyl ligands are scarce.13 We report here the synthesis
trinuclear compound [ClCu(µ-η :κP-C H PPh ) Ti(µ-η -C᎐
᎐
5 4 2 2
CBut)2CuCl] 2. The elemental analyses are in agreement with
this formulation and in addition the molecular peak observed
in the FAB possitive spectrum of 2 reveals the presence of
two CuCl fragments in the molecule. The IR spectrum in the
5
t
᎐
of new mononuclear complexes [Ti(η -C H R) (C᎐CBu ) ] (R =
᎐
5
4
2
2
J. Chem. Soc., Dalton Trans., 1999, 533–538
533

View Article Online
solid state shows a ν(C᎐C) at 1984 cmϪ1, shifted to lower
On the other hand, we thought that a possible way to force
the co-ordination of the CuCl fragment only through the
alkyne groups could be the use of [(OC)4Mo(µ-η5 :κP-
᎐
᎐
frequency after co-ordination to the copper() fragment, and
two resonances are observed in the 13C-{1H} NMR spectrum
for the acetylide carbon atoms at lower field (δ 149.8 and 134.1)
in comparison to those of the mononuclear titanium pre-
cursor. A broad signal corresponding to the PPh2 groups of
t
᎐
C H PPh ) Ti(C᎐CBu ) ] as starting material. Molybdenum(0)
᎐
5
4
2
2
2
carbonyl complexes are known to have a great tendency to bind
phosphines,19 in fact [(OC)4Mo(µ-η5 :κP-C5H4PPh2)2TiCl2] was
reported several years ago.20 That is the reason why we initially
5
2
t
᎐
complex [ClCu(µ-η :κP-C H PPh ) Ti(µ-η -C᎐CBu ) CuCl] 2,
᎐
5
4
2
2
2
5
t
᎐
only slightly shifted (δ Ϫ17.0) to higher field, is recorded in the
31P-{1H} NMR spectrum. As we will mention later, this result is
in contrast with the strong shift that this signal experiences
when a molybdenum fragment is co-ordinated to the titanium
atom through this PPh2 group, but it is in agreement with data
attempted the reaction between [Ti(η -C H PPh ) (C᎐CBu ) ]
᎐
5 4 2 2 2
1 and [Mo(CO)4(nbd)] under different conditions, obtaining
in all cases unsatisfactory results. Then a mixture of [(OC)4-
5
t
᎐
Mo(µ-η :κP-C H PPh ) TiCl ] and LiC᎐CBu was allowed to
᎐
5
4
2
2
2
react in diethyl ether at Ϫ20 ЊC to afford the new compound
1
5
t
found for other copper phosphine complexes.17 The H NMR
[(OC) Mo(µ-η :κP-C H PPh ) Ti(C᎐CBu ) ] 5 as a brown solid.
᎐
᎐
4
5
4
2
2
2
spectrum exhibits two multiplets at δ 6.08 and 5.98 and a singlet
at δ 1.35 attributable to the protons of Cp and But groups
respectively. The molecular structure of complex 2, suggested
by analytical and spectroscopic data, was confirmed by a X-ray
diffraction study.
Further reaction of complex 5 and CuCl in 1:1 stoichiometry
using thf as solvent gave the heteronuclear species [(OC)4Mo-
5
2
t
᎐
(µ-η :κP-C H PPh ) Ti(µ-η -C᎐CBu ) CuCl] 6 (Scheme 1).
᎐
5
4
2
2
2
It has been previously noted that different shifts are observed
for the signal corresponding to the PPh2 groups in the 31P-{1H}
NMR of all these compounds. While a strong downfield shift
was recorded for complexes 5 (δ 32.8) and 6 (δ 33.8) a very slight
one is exhibited by 3 (δ Ϫ10.00) and 4 (δ Ϫ9.4). Owing to the
instability in solution of compound 4 it was not possible to
run its 13C-{1H} NMR spectrum. For the rest of the compounds
the spectra show the resonances corresponding to the α- and
Irrespective of whether the reaction of complex 1 and CuCl
was carried out using 1 or 2 equivalents of CuCl only 2 was
obtained. This seems to indicate an equal tendency of the CuCl
2
᎐
moiety to co-ordinate P,P or (η -C᎐C) , although a recent
᎐
2
report18 on reactions of copper() halides and X(C᎐CBu )
t
᎐
᎐
2
(X = PPh, S, SO or SO2) ligands showed a co-ordinative prefer-
t
᎐
᎐
ence PhP > C᎐C > S.
β-carbon atoms of the C᎐CBu groups that experience a down-
᎐
᎐
Keeping in mind the idea of preparing heteronuclear species
with only a copper fragment linked to the titanocene, either
field shift in relation to that of 1, more pronounced for 6
but in both cases similar to the ones founded for analogous
acetylides.16 A stretching band appears in the IR spectra of
t
᎐
towards PPh2 or C᎐CBu groups, we studied the reaction
᎐
between [Ti(η5-C5H4PPh2)2Cl2] and CuCl in CH2Cl2. Stirring
this mixture at room temperature afforded the complex
[ClCu(µ-η5 :κP-C5H4PPh2)2TiCl2] 3. Further reaction of 3
compounds 4–6 in the C᎐C region, moved for compound 6 to
᎐
᎐
lower frequency as a consequence of the co-ordination of the
CuCl fragment to the acetylenic ligands. All these species show
t
1
᎐
with the stoichiometric amount of LiC᎐CBu in diethyl
in the Cp region of the H NMR spectra two signals shifted
᎐
ether–dichloromethane (1:3) at Ϫ20 ЊC gave [ClCu(µ-η5 :κP-
C H PPh ) Ti(C᎐CBu ) ] 4 (Scheme 1). The last reaction failed
downfield indicative of the linking of a metal fragment to the
titanium atom through the PPh2 groups.
t
᎐
᎐
5
4
2
2
2
when it was carried out using just diethyl ether. We think that
the great insolubility of complex 3 in this solvent could be the
reason for this result. Complexes 3 and 4 are very unstable in
solution, and the last also in the solid state. In fact 4 could not
be characterised by analytical data or mass spectroscopy. The
We have recently established21 how the oxidation of the Cp
substituents in [Ti(η5-C5H4PPh2)2X2] (X = Cl or SR) provokes a
significant enhancement of stability in the resulting species
[Ti{η5-C5H4P(E)Ph2}2X2] (X = Cl or SR; E = O or S). The
reactions of compound 1 and H2O2 or S8 as oxidisers led to
5
2
t
5
t
᎐
᎐
compound [ClCu(µ-η :κP-C H PPh ) Ti(µ-η -C᎐CBu ) CuCl]
complexes [Ti{η -C H P(E)Ph } (C᎐CBu ) ] (E = O 7 or S 8
᎐
᎐
5
4
2
2
2
5 4 2 2 2
2 was also obtained by addition of an equimolecular amount
of CuCl to a solution of 4.
Scheme 2), nevertheless in this case only 8 seems to be more
stable than the starting material 1.
Ph2
Ph2
P
Ph2
P
CO
P
CO
Mo
CO
Mo
OC
OC
2LiC CBut
Et2O
OC
OC
OC
OC
Cl
Cl
CuCl
thf
Mo
CO
CuCl
Ti
Ti
Ti
CO
P
CO
P
P
Ph2
Ph2
Ph2
6
5
Mo(CO)4(nbd)
Ph2
P
Ph2
P
PPh2
Cl
CuCl
thf
2LiC CBut
CH2Cl2
Cl
Ti
ClCu
ClCu
Ti
Ti
Cl
Cl
P
P
Ph2
Ph2
PPh2
3
4
2LiC CBut
thf
CuCl
Et2O
Ph2
P
PPh2
Ti
CuCl
thf
ClCu
CuCl
Ti
P
Ph2
PPh2
1
2
Scheme 1
534
J. Chem. Soc., Dalton Trans., 1999, 533–538

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PPh2
Ti
E
PPh2
E
PPh2
PPh2
H2O2 or S8
thf
1
CuCl
thf
CuCl
Ti
Ti
PPh2
PPh2
E
E
E = O 7
E = S
E = O 9
E = S 10
8
Scheme 2
The soft base character of a sulfur donor ligand, as well
as the existence of some examples on complexes of CuI with
phosphine oxides,22 prompted us to study the co-ordination
chemistry of phosphoryl- and thiophosphoryl-cyclo-
pentadienyl derivatives 7 and 8 with CuCl. Although there have
been reported several complexes where CuCl co-ordinates to
oxygen and sulfur atoms of [Fe{η5-C5H4P(E)Ph2}2] [E = O
(dpopf) or S (dptpf)],13 in our case no evidence has been
observed of co-ordination through these atoms, the copper
fragment showing a preference for the alkyne ligands to give
Fig. 1 An ORTEP drawing and atom numbering scheme of the
complex 2.
Table 1 Selected bond lengths (Å) and angles (Њ) of complex 2
heterodinuclear
compounds
[{η5-C5H4P(E)Ph2}2Ti(µ-η2-
Cu(1)–Ti(1)
Cu(1)–Cl(1)
Cu(1)–C(1)
Cu(1)–C(2)
Cu(1)–C(3)
Cu(1)–C(4)
Cu(2)-Cl(2)
Cu(2)–P(1)
Cu(2)–P(2)
C(1)–C(2)
2.899(4)
2.180(6)
2.12(2)
2.23(2)
2.06(2)
2.22(2)
2.219(6)
2.279(6)
2.259(5)
1.28(2)
2.02(2)
Ti(1)–C(3)
C(3)–C(4)
Ti(1)–Cp(1)
Ti(1)–Cp(2)
2.15(2)
1.18(3)
2.0491
2.0671
t
᎐
C᎐CBu ) CuCl] (E = O 9 or S 10 Scheme 2).
᎐
2
Compounds 7–10 have been characterised by spectroscopic
and analytical techniques. The presence of phosphoryl and
thiophosphoryl groups in the Cp rings of complexes 7 and 8
Cp(1)–Ti(1)–Cp(2)
C(1)–Ti(1)–C(3)
Ti(1)–C(1)–C(2)
C(1)–C(2)–C(5)
Ti(1)–C(3)–C(4)
C(3)–C(4)–C(9)
135.5
1
provokes a downfield shift of these proton signals in the H
92.2(8)
165(2)
162(2)
169(2)
163(2)
NMR spectra (δ 7.01 and 6.51 7 and 6.95 and 6.50 8) compared
to those of the starting material 1 (δ 6.24 and 6.12). The same
tendency is observed in the 31P-{1H} NMR spectra (δ 23.9 7
and 34.7 8) consistent with the oxidation of PIII to PV, however
the signals are only slightly shifted for complexes 9 and 10
suggesting the non-co-ordination of the CuCl fragment to these
groups.
The instability in solution of complex 7 does not allow the
acquisition of satisfactory analytical data or a 13C-{1H} NMR
spectrum. For 8 two resonances for the acetylenic carbons are
obtained in the range expected, while for 9 and 10 the same
signals are shifted downfield by co-ordination of the CuCl
Ti(1)–C(1)
5
analogous complexes [(η -C H SiMe ) Ti(C᎐CPh) CuCl]24 and
᎐
᎐
5
4
3
2
2
5
9
᎐
᎐
[(η -C H SiMe ) Ti(C᎐CSiMe ) CuX] (X = C᎐CSiMe or Cl)
᎐
᎐
5
4
3
2
3
2
3
the Ti–C(1) [2.02(2) Å] and C(1)–C(2) [1.28(2) Å] distances are
slightly different. The smaller Ti–C(1) bond value is probably
due to a π interaction along the σ bond between the titanium
t
᎐
and the C᎐CBu group, as has been indicated for the compound
᎐
5
2
25
᎐
[(η -C H ) Ti(µ-σ:η -C᎐CPh)(µ-PPh )Ni(PPh )]
where
a
᎐
5
5
2
2
3
fragments to these groups. In addition for 9 and 10 the IR
Ti–C distance of 2.065(8) Å has been reported. The least
squares plane defined by TiC4CuCl shows a deviation of 0.0229
᎐
spectra show a modification of the C᎐C stretching frequency,
᎐
while the ν (P᎐E) (E = O or S) remains almost unchanged.
᎐
Å, indicating a tweezer interaction between the copper atom
t
and the [Ti](C᎐CBu ) entity.9,11 In addition a C(1)–Ti–C(3)
᎐
᎐
2
Crystal structure of complex 2
angle of 92.2(8)Њ is similar to that found in the above mentioned
An ORTEP23 drawing of the molecular structure showing
the atom numbering scheme is presented in Fig. 1. Selected
bond distances and angles are collected in Table 1.
complex and other related compounds.16
The Ti–Cu distance of 2.899(4) Å is the shortest found, as
far as we know, in acetylide derivatives of this type [(η5-
C H SiMe ) Ti(C᎐CSiMe ) CuR] {R = Cl [2.9645(5) Å];9
᎐
The titanium atom lies in a pseudo-tetrahedral environment
involving the two cyclopentadienyl rings and the two acetylide
ligands and both copper atoms show a distorted trigonal planar
geometry. Atom Cu(1) is surrounded by the two η2-bonded
᎐
5
᎐
4
3
2
3
26
2
C᎐CSiMe [2.9665(8) Å]; or C6H2Me3-2,4,6 [2.9418(5) Å]16b
}
᎐
3
but it is quite close to that reported for the compound
5
24
᎐
[(η -C H SiMe ) Ti(C᎐CPh) CuCl] [2.909(3) Å]. Although
᎐
5
4
3
2
2
t
᎐
C᎐CBu groups and the chloride ligand. Although crystal data
this bond distance is slightly greater than the sum of covalent
radii it could suggest a weak interaction between the two metal
centres.
᎐
5
t
᎐
for the precursor [Ti(η -C H PPh ) (C᎐CBu ) ] 1 are not
available, the Ti–C᎐C and C᎐C–C angles [165(2), 169(2) and
᎐
5
᎐
4
2
2
2
᎐
᎐
᎐
162(2), 163(2)Њ] in complex 2 are shifted from the linearity
The Cu(2) centre is co-ordinated to the PPh2 groups of the
phosphinocyclopentadienyl ligands and a chlorine atom. The
two Cu–P bond distances [2.279(6) and 2.259(5) Å] are slightly
different and the P(1)-Cu(2)-P(2) angle of 119.1(2)Њ is smaller
than those found in complexes P2CuX [P = PPh3 (126.9Њ);27
PPh2(C6H4Me-o) (126Њ);28 or PCy3 (134.06Њ)29], due to the fact
that the titanium precursor is acting as a chelate ligand.
The Cu–Cl distances [2.180(6) and 2.219(6) Å] found for this
complex are in agreement with normal Cu–Cl bond distances
observed in the analogous acetylide titanocene [Ti(η5-
C H SiMe ) (C᎐CSiMe ) ]16a as a result of the co-ordination to
᎐
᎐
5
4
3
2
3 2
the Group 11 metal.
᎐
It is noteworthy that the different Ti–C and C᎐C distances for
᎐
each alkyne group suggest that although both of them are η2
bonded to the copper atom, the strength of the interaction is
not the same. Thus, whereas the Ti–C(3) [2.15(2) Å] and C(3)-
C(4) [1.18(3) Å] distances are in the range observed for other
J. Chem. Soc., Dalton Trans., 1999, 533–538
535

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and in the range observed for other heterodinuclear Ti–Cu
derivatives.16
from dichloromethane–methanol (1:1) afforded red needles
of 2 (0.24 g, 47%) (Found: C, 60.14; H, 5.22. C46H46Cl2Cu2P2-
TiؒCH3OH requires C, 60.21 ; H, 5.33%). νmax/cmϪ1 1984 (C᎐C).
᎐
᎐
1H NMR (CDCl3): δ 7.86–7.34 (m, 20 H, C6H5), 6.08 (m, 4 H,
Conclusion
C5H4), 5.98 (m, 4 H, C5H4) and 1.35 (s, 18 H, But). 31P-{1H}
5
t
5
4
2
2
2
NMR (CDCl3): δ Ϫ17.0 (s, br, PPh2). 13C-{1H} NMR (CDCl3):
᎐
The complex [Ti(η -C H PPh ) (C᎐CBu ) ] behaves as
a
᎐
t
᎐
metalloligand through both C᎐CBu and PPh2 groups. A
᎐
᎐
᎐
δ 149.8 (s, C᎐C), 134.1 (s, C᎐C), 133.0-128.3 (m, C H ), 127.6
᎐
᎐
6
5
different behaviour of [Ti(η5-C5H4PPh2)2Cl2] and [Ti(η5-
(d, JPC = 9.9, i-C of C5H4), 114.7, 113.2 (m, JPC = 12.8 Hz, o-,
m-C of C5H4), 30.7 [s, C(CH3)] and 30.0 (CH3). FAB-MS:
m/z 906, Mϩ; 871, [M Ϫ Cl]ϩ; 807, [M Ϫ CuCl]ϩ; and 708,
[M Ϫ 2CuCl]ϩ.
t
᎐
C H PPh ) (C᎐CBu ) ] has been observed, thus it has been
᎐
5
4
2
2
2
reported that [(OC)4Mo(µ-η5 :κP-C5H4PPh2)2TiCl2] is obtained
by reaction of [Ti(η5-C5H4PPh2)2Cl2] and [Mo(CO)4(nbd)],
however we have found that the same molybdenum reagent
5
t
5
4
2
2
2
[ClCu(ì-ç5 :êP-C5H4PPh2)2TiCl2] 3. To a dichloromethane
solution (30 cm3) of [Ti(η5-C5H4PPh2)2Cl2] (0.40 g, 0.64 mmol)
was added (CuCl)n (0.06 g, 0.64 mmol) and the mixture stirred
for 1 h in the darkness. The resulting brown solution was
filtered through Celite and then concentrated (ca. 10 cm3).
Addition of n-hexane (15 cm3) afforded a brown solid that was
washed with several portions of n-hexane (3 × 5 cm3) and dried
under vacuum (0.38 g, 80%) (Found: C, 56.35; H, 3.51.
C34H28Cl3CuP2Ti requires C, 57.01; H, 3.94%). 1H NMR
(CDCl3): δ 7.75–7.40 (m, 20 H, C6H5), 6.74 (m, 4 H, C5H4) and
6.65 (m, 4 H, C5H4). 31P-{1H} NMR (CDCl3): δ Ϫ10.0 (s, PPh2).
᎐
does not react when [Ti(η -C H PPh ) (C᎐CBu ) ] is used as
᎐
starting material.
On the other hand, CuCl acts as a Lewis acid towards the
PPh2 groups to afford the complex [ClCu(µ-η5 :κP-C5H4-
PPh2)2TiCl2], but we have not been able to isolate the hetero-
5
t
᎐
dinuclear species [ClCu(µ-η :κP-C H PPh ) Ti(C᎐CBu ) ] or
᎐
5
4
2
2
2
5
2
t
5
᎐
[(η -C H PPh ) Ti(µ-η -C᎐CBu ) CuCl] by reaction of [Ti(η -
᎐
5
4
2
2
2
t
᎐
C H PPh ) (C᎐CBu ) ] and CuCl. No selective co-ordination
᎐
5
4
2
2
2
has been found in the last reaction and [ClCu(µ-η5 :κP-
2
t
᎐
C H PPh ) Ti(µ-η -C᎐CBu ) CuCl] was the sole compound
᎐
5
4
2
2
2
obtained under all conditions we have studied.
Finally, the stability of the complex [Ti(η5-C5H4PPh2)2-
t
5
t
᎐
(C᎐CBu ) ] does not increase by oxidation of the PPh groups,
᎐
᎐
2
2
[ClCu(ì-ç :êP-C H PPh ) Ti(C᎐CBu ) ] 4. To a solution
᎐
5 4 2 2 2
of LiBun (0.40 cm3, 0.65 mmol) in ether (25 cm3) at Ϫ20 ЊC
was added HC᎐CBu (0.08 cm , 0.65 mmol). The mixture was
in contrast to the enhancement observed for the analogous
thiolate derivatives [Ti{η5-C5H4P(E)Ph2}2(SR)2] (E = O or S).
t
3
᎐
᎐
stirred for 5 min, then a solution of complex 3 (0.21 g, 0.30
mmol) in dichloromethane (15 cm3) was added. After stirring
for 45 min the resulting solution was filtered over Celite and
the solvent removed in vacuo to give the brown compound
Experimental
Reactions were carried out under an atmosphere of argon by
means of conventional Schlenk techniques.30 Solvents were
purified according to standard procedures.31 The complexes
[Ti(η5-C5H4PPh2)2Cl2],3[(OC)4Mo(µ-η5 :κP-C5H4PPh2)2TiCl2]20
and [Mo(CO)4(nbd)]32 were prepared as previously published.
All other reagents were used as obtained commercially. Micro-
analyses were determined with a Perkin-Elmer 2400 micro-
analyser. Infrared spectra (thf solution or KBr) were recorded
on a Perkin-Elmer 1600 FT spectrophotometer, NMR spectra
on Bruker AMX-300 or -400 spectrometers with chemical shifts
reported in ppm relative to external standards (SiMe4 for
1H and 13C and H3PO4 for 31P) and mass spectra (FABϩ) on a
VG Autospec spectrometer.
5
t
[ClCu(µ-η :κP-C H PPh ) Ti(C᎐CBu ) ] 4 (70%). νmax/cmϪ1
᎐
᎐
5
4
2
2
2
1
᎐
2072 (C᎐C). H NMR (CDCl ): δ 7.57–7.15 (m, 20 H, C H ),
᎐
3
6
5
6.19 (m, 4 H, C5H4), 6.05 (m, 4 H, C5H4) and 1.16 (s, 18 H, But).
31P-{1H} NMR (CDCl3): δ Ϫ9.4 (s, PPh2). Complex 4 could not
be characterised by elemental analyses and mass spectroscopy
due to its instability in solution.
5
t
᎐
[(OC) Mo(ì-ç :êP-C H PPh ) Ti(C᎐CBu ) ] 5. This com-
᎐
4
5
4
2
2
2
pound was obtained following the procedure described for 1
by reaction of [(OC)4Mo(µ-η5 :κP-C5H4PPh2)2TiCl2] and LiC-
t
᎐
᎐CBu (70%) (Found: C, 64.98; H, 5.02. C50H46MoO4P2Ti
᎐
requires C, 65.51; H, 5.06%). νmax/cmϪ1 2069 (C᎐C); (thf
solution) 2019m, 1920s and 1896vs (CO). H NMR (CDCl3):
᎐
᎐
1
Syntheses
δ 7.57–7.15 (m, 20 H, C6H5), 6.87 (q, 4 H, C5H4), 6.34 (q, 4 H,
C5H4) and 1.11 (s, 18 H, But). 31P-{1H} NMR (CDCl3): δ 32.8
(s, PPh2). 13C-{1H} NMR (CDCl3): δ 214.2 (m, COeq), 209.6
5
t
᎐
[Ti(ç -C H PPh ) (C᎐CBu ) ] 1. To a diethyl ether solution
᎐
5
4
2
2
2
3
t
3
᎐
(20 cm ) of HC᎐CBu (0.10 cm , 0.84 mmol) cooled at Ϫ20 ЊC
᎐
was added dropwise LiBun (0.52 cm3, 0.84 mmol). After 10 min
of stirring [Ti(η5-C5H4PPh2)2Cl2] (0.25 g, 0.40 mmol) was added
and subsequently the cooling bath removed. Stirring at
room temperature was maintained for 1 h. Concentration and
filtration of the solution through Celite afforded complex 1 as
an orange-brown crystalline solid after evaporation of the
solvent to dryness (0.23 g, 83%) (Found: C, 77.80; H, 6.38.
᎐
(t, CO ), 139.7 (s, C᎐C), 135.1–127.7 (m, C H ), 127.3 (d,
᎐
ax
6
5
᎐
JPC = 9.5, i-C of C H ), 123.5 (s, C᎐C), 121.3 (m, m-C of C H ),
᎐
5
4
5
4
117.7 (t, JPC = 5.8 Hz, o-C of C5H4), 31.1 (CH3) and 28.7
[s, C(CH3)]. FAB-MS: m/z 916, Mϩ; 888, [M Ϫ CO]ϩ; 860,
ϩ
t ϩ
ϩ
᎐
[M Ϫ 2CO] ; 835, [M Ϫ C᎐CBu ] ; 832, [M Ϫ 3CO] ; 804,
᎐
ϩ
t ϩ
᎐
[M Ϫ 4CO] ; 754, [M Ϫ 2C᎐CBu ] ; and 708, [M Ϫ Mo-
᎐
(CO)4]ϩ.
C46H46P2Ti requires C, 77.96 ; H, 6.54%). νmax/cmϪ1 2069 (C᎐C).
᎐
᎐
5
2
t
1H NMR (CDCl3): δ 7.40–7.27 (m, 20 H, C6H5), 6.24 (m, 4 H,
᎐
[(OC) Mo(ì-ç :êP-C H PPh ) Ti(ì-ç -C᎐CBu ) CuCl]
6.
᎐
4
5
4
2
2
2
To a thf solution (30 cm3) of complex 5 (0.25 g, 0.27 mmol)
was added (CuCl)n (0.03 g, 0.27 mmol). After 1.5 h of stirring
in the darkness the resulting solution was filtered through
Celite and the solvent removed under vacuum. The residue was
recrystallised from thf–pentane (1:1) at Ϫ20 ЊC to yield an
orange solid corresponding to 6 (0.17 g, 55%) (Found: C, 59.22;
H, 4.51. C50H46ClCuMoO4P2Ti requires C, 59.13; H, 4.56%);
C5H4), 6.12 (m, 4 H, C5H4) and 1.14 (s, 18 H, But). 31P-{1H}
NMR (CDCl3): δ Ϫ15.1 (s, PPh2). 13C-{1H} NMR (CDCl3):
᎐
δ 138.3–128.0 (m, C H ), 138.2 (s, C᎐C), 122.1 (t, JPC = 12.8 Hz
o-C of C5H4), 118.4 (t, JPC = 10.3, m-C of C5H4), i-C of C5H4
not observed, 115.8 (s, C᎐C), 31.0 (CH ) and 30.6 [s, C(CH )].
᎐
6
5
᎐
᎐
3
3
ϩ
t ϩ
᎐
FAB-MS: m/z 708, M ; 627, [M Ϫ C᎐CBu ] ; and 546, [M Ϫ
᎐
t ϩ
᎐
2C᎐CBu ] .
᎐
νmax/cmϪ1 1995 (C᎐C); (thf solution): 2017m, 1922m and 1896vs
᎐
᎐
5
2
t
1
᎐
[ClCu(ì-ç :êP-C H PPh ) Ti(ì-ç -C᎐CBu ) CuCl] 2. To a
(CO). H NMR (CDCl3): δ 7.48–7.39 (m, 20 H, C6H5), 6.25
᎐
5
4
2
2
2
solution of complex 1 (0.40 g, 0.56 mmol) in thf (25 cm3) was
added (CuCl)n (0.05 g, 0.56 mmol). The mixture was stirred in
the darkness for 2 h and then the solvent removed in vacuo. The
solid residue was purified by chromatography on silica gel 100.
A red band was eluted from hexane–thf (1:1). Recrystallisation
(m, 4 H, C5H4), 6.05 (m, 4 H, C5H4) and 1.40 (s, 18 H, But). 31P-
{1H} NMR (CDCl3): δ 33.8 (s, PPh2). 13C-{1H} NMR (CDCl3):
᎐
δ 213.8 (m, CO ), 209.5 (t, J = 8.6, CO ), 152.6 (s, C᎐C),
᎐
eq
ax
᎐
135.5 (s, C᎐C), 133.4 (d, JPC = 15.2, i-C of C5H4), 132.5–128.3
᎐
(m, C6H5), 117.8 (s, m-C of C5H4), 114.6 (t, JPC = 6.0 Hz, o-C of
536
J. Chem. Soc., Dalton Trans., 1999, 533–538

View Article Online
Table 2 Crystal data and structure refinement for [ClCu(µ-η5 :κP-
C5H4), 31.8 [s, C(CH3)] and 30.7 (CH3). FAB-MS: m/z 1015,
Mϩ; 987, [M Ϫ CO]ϩ; 980, [M Ϫ Cl]ϩ; 959, [M Ϫ 2CO]ϩ; 932,
[M Ϫ 3CO]ϩ; 916, [M Ϫ CuCl]ϩ; 904, [M Ϫ 4CO]ϩ and 808,
[M-Mo(CO)4]ϩ.
2
t
᎐
C5H4PPh2)2Ti(µ-η -C᎐CBu )2CuCl] 2
᎐
Empirical Formula
M
C47H50Cl2Cu2OP2T
938.76
Crystal system
Space group
a/Å
b/Å
Orthorhombic
Pna21 (no. 33)
28.989(8)
14.109(4)
10.606(2)
4337(1)
4
1.44
0.042
1936
1.383
3424
3424
1904
1904/0/255
0.064, 0.083
5
t
᎐
[Ti{ç -C H P(O)Ph } (C᎐CBu ) ] 7. To a solution of com-
᎐
5
4
2
2
2
plex 1 (0.25 g, 0.32 mmol) in thf (30 cm3) was added a 30%
solution of H2O2 (0.02 cm3, 0.32 mmol), and the mixture stirred
for 30 min. Then the solution was filtered through Celite and
the solvent removed to dryness (0.16 g, 70%). νmax/cmϪ1 2064
c/Å
U/Å3
(C᎐C) and 1178 (P᎐O). 1H NMR (CDCl3): δ 7.65–7.26 (m,
Z
᎐
᎐
᎐
Dc/Mg mϪ3
20 H, C6H5), 7.01 (m, 4 H, C5H4), 6.51 (m, 4 H, C5H4) and 0.95
(s, 18 H, But). 31P-{1H} NMR (CDCl3): δ 23.9 [s, P(O)Ph2].
Complex 7 could not be characterised by elemental analyses
and mass spectroscopy due to its instability in solution.
Rint
F(000)
µ(Mo-Kα)mmϪ1
Reflections collected
Unique reflections
No. reflections [I > 3.5σ(I)]
Data/restraints/parameters
Residuals R, RЈ
5
t
᎐
[Ti{ç -C H P(S)Ph } (C᎐CBu ) ] 8. To a solution of complex
᎐
5
4
2
2
2
1 (0.25 g, 0.32 mmol) in thf (30 cm3) at 0 ЊC was added S8
(0.0262 g, 0.08 mmol). After stirring for 30 min the solution was
filtered through Celite and the solvent removed (0.21 g, 85%)
(Found: C, 71.52; H, 5.88. C46H46P2S2Ti requires C, 71.49; H,
Calculations were performed on a VAXstation 3520 computer
applying the TEXSAN 5.0 software33 and in the later stages
on a Silicon Graphics Indigo 2 Extreme computer with the
TEXSAN 1.7 package.34
Relevant crystallographic data are listed in Table 2. Unit
cell dimensions were determined by applying the setting angles
of 25 high-angle reflections. Three standard reflections were
monitored during the data collection, showing no significant
variance. The intensities were corrected for absorption by
applying Ψ scans of several reflections with the transmission
factors within the range 0.92–1.00.
6.00%). νmax/cmϪ1: 2067 (C᎐C) and 653 (P᎐S). 1H NMR
᎐
᎐
᎐
(CDCl3): δ 7.65–7.42 (m, 20 H, C6H5), 6.95 (m, 4 H, C5H4), 6.50
(m, 4 H, C5H4) and 1.00 (s, 18 H, But). 31P-{1H} NMR (CDCl3):
13
1
᎐
δ 34.7 [s, P(S)Ph2]. C-{ H} NMR (CDCl ): δ 140.7 (s, C᎐C),
᎐
3
135.7 (d, JPC = 10.2, i-C of C5H4), 134.4–128.2 (m, C6H5), 121.6,
119.5 (d, JPC = 10.5 Hz, overlapping doublets, o-C of C5H4),
᎐
118.8 (s, C᎐C), 113.4, 112.7 (s, m-C of C H ), 31.4 (CH ) and
᎐
5
4
3
ϩ
t ϩ
᎐
28.9 [s, C(CH )]. FAB-MS: m/z 772, M ; 691, [M Ϫ C᎐CBu ] ;
659, [M Ϫ S Ϫ C᎐CBu ] ; and 610, [M Ϫ 2C᎐CBu ] .
᎐
t ϩ
3
t ϩ
᎐
᎐
᎐
᎐
5
2
t
᎐
The structures were solved by direct methods in SIR 92.35
Full-matrix least-squares refinement with anisotropic thermal
displacement parameters for the Cu, Ti, Cl and P atoms
yielded the final R of 0.064. The hydrogen atoms were found
in the Fourier-difference maps and included in the calculations
without further refinement . The goodness of fit has a value of
S = 1.95. A total of 3424 reflections were collected, covering
indices 0 р h р 16, 0 р k р 32 and 0 р l р 12. The final
electron density map was essentially featureless with the highest
[{ç -C H P(O)Ph } Ti(ì-ç -C᎐CBu ) CuCl] 9. To
a thf
᎐
5
4
2
2
2
solution (30 cm3) of complex 7 (0.35 g, 0.47 mmol) was added
(CuCl)n (0.0465 g, 0.47 mmol) and the mixture stirred for 1 h
in the darkness. Subsequently the solvent was removed and the
residue chromatographed on silica gel 100. A red band was
eluted by thf–hexane (2:1) to yield a solid that afforded
red needles of complex 9 after recrystallisation from dichloro-
methane–methanol (1:1) (0.25 g, 65%) (Found: C, 64.56; H,
5.77. C46H46ClCuO2P2TiؒCH3OH requires C, 64.76; H, 5.78%).
νmax/cmϪ1 1986 (C᎐C) and 1176 (P᎐O). 1H NMR (CDCl3):
᎐
peak of 0.75 e ÅϪ3
.
᎐
᎐
δ 7.62–7.46 (m, 20 H, C6H5), 6.63 (q, 4 H, C5H4), 6.10 (q, 4 H,
CCDC reference number 186/1295.
C5H4) and 1.25 (s, 18 H, But). 31P-{1H} NMR (CDCl3): δ 20.7
13
1
᎐
[s, P(O)Ph2]. C-{ H} NMR (CDCl ): δ 150.8 (s, C᎐C),
᎐
3
Acknowledgements
᎐
134.7 (s, C᎐C), 134.0-128.4 (m, C H ), 132.9 (t, JPC = 17.0
᎐
6
5
Hz, i-C of C5H4), 115.5, 113.8 (s, o-, m-C of C5H4), 31.6
We thank the Dirección General de Investigación Científica
y Técnica (Spain) (Projects PB93-0250 and PB95-0003-CO2-01-
02) and the University of La Rioja (Project API-98/B16) for
financial support. We thank Dr Esther García (University of
Oviedo) for NMR help.
[s, C(CH3)] and 30.8 (CH3). FAB-MS: m/z 839, Mϩ; 803,
ϩ
t ϩ
᎐
[M Ϫ Cl] ; and 659, [M Ϫ CuCl Ϫ C᎐CBu ] .
᎐
5
2
t
᎐
[{ç -C H P(S)Ph } Ti(ì-ç -C᎐CBu ) CuCl] 10. This complex
᎐
5
4
2
2
2
was synthesized following the above procedure by reaction
between 8 and (CuCl)n (67%) (Found: C, 63.45; H, 5.18.
C46H46ClCuP2S2Ti requires C, 63.37; H, 5.32%); νmax/cmϪ1 1986
References
1
᎐
(C᎐C) and 654 (P᎐S). H NMR (CDCl ): δ 7.63–7.45 (m, 20 H,
᎐
᎐
3
1 U. Amador, E. Delgado, J. Forniés, E. Hernández, E. Lalinde and
M. T. Moreno, Inorg. Chem., 1995, 34, 5279.
2 I. Ara, E. Delgado, J. Forniés, E. Hernández, E. Lalinde,
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But). 31P-{1H} NMR (CDCl3): δ 34.1 [s, P(S)Ph2]. 13C-{1H}
᎐
᎐
NMR (50 MHz, CDCl ): δ 149.6 (s, C᎐C), 134.7 (s, C᎐C),
᎐
᎐
3
133.6–128.8 (m, C6H5), 127.5 (d, JPC = 9.5, i-C of C5H4), 118.6,
115.6 (d, JPC= 10.2 Hz, o-, m-C of C5H4), 32.0 [s, C(CH3)] and
30.8 (s, CH3). FAB-MS: m/z 871, Mϩ; 835, [M Ϫ Cl]ϩ; 691,
t ϩ
t ϩ
᎐
᎐
[M Ϫ CuCl Ϫ C᎐CBu ] ; and 610, [M Ϫ CuCl Ϫ 2C᎐CBu ] .
᎐
᎐
5 R. Nast, Coord. Chem. Rev., 1982, 47, 89; A. J. Carty, Pure Appl.
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Crystal structure of complex 2
Crystals of complex 2 suitable for X-ray analysis were grown as
very thin red needles by slow diffusion of methanol into a
dichloromethane solution of the compound. A crystal of
dimensions 0.08 × 0.08 × 0.36 mm was selected for the data
collection. All X-ray measurements were carried out on a
Rigaku AFC6S diffractometer at 173 K using Mo-Kα radiation
(λ = 0.71069 Å). The diffraction peaks were generally weak.
8 J. R. Berenguer, J. Forniés, E. Lalinde and A. Martín, Angew.
Chem., Int. Ed. Engl., 1994, 33, 2083.
J. Chem. Soc., Dalton Trans., 1999, 533–538
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25 S. Pulst, P. Arndt, W. Baumann, A. Tillack, R. Kempe and
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