Electron rich bidentate phosphinimine-imine ligands: Synthesis and reactivity of late transition metal complexes

Article abstract of DOI:10.1039/b912783f

Electron rich phosphinimine-imine proligands Ph₃PN(C ₆H₄)C(Ph)(NAr) (L_Ar) (Ar = 4-(OEt)C ₆H₄ (OEt), 3,5-Me₂C₆H ₃(Xyl)) were synthesized in three steps from 2-aminobenzophenone. These compounds, along with previously reported L_Mes and L _Tol (Mes = 2,4,6-Me₃C₆H₂, Tol = 4-MeC₆H₄) were used to synthesize a series of tetracarbonyltungsten(0) complexes: L_MesW(CO)₄ (1), L _TolW(CO)₄ (2), L_OEtW(CO)₄ (3), and L_XylW(CO)₄ (4). The ligands were evaluated by analysis of the carbonyl stretching frequencies of the tungsten complexes and were shown to be better σ-donors and poorer π-acceptors compared to similar ligands in the literature. The coordination chemistry of the proligands was expanded to other late transition metals and L_MesCoCl₂ (5), L _TolCoCl₂ (6), L_MesNiBr₂ (7), L _TolNiBr₂ (8), L_MesZnCl₂ (9), and L_TolZnCl₂ (10) were synthesized by the direct reaction of L_Mes and L_Tol with the respective metal dihalide precursors. The complexes were fully characterized and the molecular structures of complexes 3, 6, 7, and 10 were reported. The synthesis of zinc complexes 9 and 10 was dependent on the steric bulk of the ligand. Complex 10 proved to be resistant to derivatization via a number of routes. The Royal Society of Chemistry.

Full text of DOI:10.1039/b912783f

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www.rsc.org/dalton | Dalton Transactions
Electron rich bidentate phosphinimine-imine ligands: Synthesis and reactivity
of late transition metal complexes†
Christopher J. Wallis, Ira L. Kraft, Brian O. Patrick and Parisa Mehrkhodavandi*
Received 30th June 2009, Accepted 28th August 2009
First published as an Advance Article on the web 25th September 2009
DOI: 10.1039/b912783f
Electron rich phosphinimine-imine proligands Ph3PN(C6H4)C(Ph)(NAr) (LAr) (Ar = 4-(OEt)C6H4
(OEt), 3,5-Me2C6H3(Xyl)) were synthesized in three steps from 2-aminobenzophenone. These
compounds, along with previously reported LMes and LTol (Mes = 2,4,6-Me3C6H2, Tol = 4-MeC6H4)
were used to synthesize a series of tetracarbonyltungsten(0) complexes: LMesW(CO)4 (1), LTol W(CO)4
(2), LOEtW(CO)4 (3), and LXylW(CO)4 (4). The ligands were evaluated by analysis of the carbonyl
stretching frequencies of the tungsten complexes and were shown to be better s-donors and poorer
p-acceptors compared to similar ligands in the literature. The coordination chemistry of the proligands
was expanded to other late transition metals and LMesCoCl2 (5), LTol CoCl2 (6), LMesNiBr2 (7), LTol NiBr2
(8), LMesZnCl2 (9), and LTol ZnCl2 (10) were synthesized by the direct reaction of LMes and LTol with the
respective metal dihalide precursors. The complexes were fully characterized and the molecular
structures of complexes 3, 6, 7, and 10 were reported. The synthesis of zinc complexes 9 and 10 was
dependent on the steric bulk of the ligand. Complex 10 proved to be resistant to derivatization via a
number of routes.
ultimately investigate the synthesis and reactivity of their zinc
complexes.
Introduction
In the last decade the chemistry of bidentate phosphinimine
ligands has expanded to encompass early1 and late2 transi-
Results and discussion
tion metals as well as main group elements and a variety of
transformations involving these compounds have been reported.3
Bisphosphinimine complexes of rhodium and palladium incor-
porating a ferrocene backbone have shown interesting reac-
tivity and catalytic behaviour.2 Phosphinimines derived from
1,1-diphosphinomethanes have been used to generate carbenoids
for a variety of metals.4 Bidentate phosphinimine-donor systems
incorporating pyridine, imidazole,5 and pyrazole6 donor moieties,
and a tridentate bisphosphinimine-pyridine7 system have also been
studied and in most cases their activity in ethylene polymerization8
was investigated. Orthopalladation of phosphinimines offers a
facile route to asymmetric pincer complexes and has been studied
in some detail.9
We have recently reported palladium complexes bearing biden-
tate phosphinimine-imine ligands and elucidated a method for
their orthopalladation and the direct and controlled reverse
reaction.10 In the context of our work with phosphinimine ligands,
as well as our efforts to develop catalysts for the controlled
polymerization of lactide,11 we were inspired by reports of cationic
zinc catalysts supported by bidentate phosphinimines for polymer-
ization of lactide.12 In this report we present our investigations into
expanding the family of phosphinimine-imine proligands, probe
their electronic properties via synthesis of carbonyl complexes,
evaluate their viability as ligands for late transition metals, and
Tunable bidentate phosphinimine-imine ligands
We have reported a facile and modular route for the synthe-
sis of a family of proligands Ph3PN(C6H4)C(Ph)(NAr) (LAr)
with a range of steric and electronic characteristics.10 The
reported compounds, LMes and LTol (Mes = 2,4,6-Me3C6H2,
Tol = p-MeC6H4) and the new compounds LOEt and LXyl
(OEt = p-(OEt)C6H4, Xyl = 3,5-Me2C6H3) are synthesized
in four steps from 2-aminobenzophenone via a 2-(triphenyl-
phosphinimine)benzophenone intermediate (Scheme 1). The
imine moieties are installed via condensation reactions of this
intermediate with p-ethoxy and 3,5-dimethylanilines to yield LOEt
and LXyl as air and moisture stable yellow solids in 85 and 81%
yield, respectively. The condensation reaction is more facile with
less hindered anilines: LTol and LOEt are synthesized in 24 h,
while LXyl and LMes require 48 h reaction time with a Dean–Stark
apparatus. We reported that the molecular structure of LMes shows
hindered rotation around the N–Ar bond and in solution two
magnetically nonequivalent ortho methyl groups are observed in
1
the H NMR spectrum.10 A similarly hindered rotation is not
1
observed for LOEt or LXyl; the H NMR spectrum of LOEt does
not show asymmetric -OCH2CH3 protons and only one signal
University of British Columbia, Department of Chemistry, 2036 Main Mall,
Vancouver, B.C., Canada. E-mail: mehr@chem.ubc.ca; Tel: 604-822-1882
† CCDC reference numbers 738462–738465. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b912783f
Scheme 1
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 541–547 | 541
©

1
Table 1 Comparison of 31{ H} NMR and IR spectroscopic characteris-
complexes. Complex 1 shows restricted rotation of the mesityl
imine moiety as observed in LMes. The two inequivalent ortho
methyl groups are observed at 1.82 and 2.50 ppm. In contrast
the xylyl derivative 4, which shows no sign of hindered rotation in
the free ligand, shows two inequivalent peaks for the meta methyl
groups at 2.06 and 2.29 ppm. The less sterically encumbered
complexes 2 and 3 show no signs of hindered rotation upon
coordination to the tetracarbonyltungsten(0) moiety.
The molecular structure of 3, obtained via single crystal X-ray
crystallography, shows distorted octahedral geometry around the
tungsten centre (Fig. 1, Table 2).15 The strained geometry of the
ligand is apparent in the twist in the ligand backbone and in the
N1–W–N2 bond angle of 76.2◦, the W–N2–C1–C6 torsion angle
of 8.5◦, and the C1–C6–C7–N2 torsion angle of 42.1◦. The W–N1
tics of compounds in this work and literature compounds
31P{ H} vPN
1
Entry Compound
(ppm)
(cm-1) vCO (cm-1)
1
2
3
4
5a
6
LMes
LTol
LOEt
LXyl
1.16
0.87
1.64
2.18
-1.38
27.36
1339
1360
1345
1328
=
Ph2PCH2(Ph)2P N(SiMe3)
1310
1
1228 1994, 1870,
1845, 1808.
1242 1996, 1870,
1846, 1805.
1231 1995, 1879,
1852, 1802.
1241 1998, 1874,
1842, 1808.
1120 2007, 1920,
1884, 1866.
2008, 1990,
1891, 1842.
2005, 1920,
1870, 1812.
1238
7
8
9
2
25.34
28.6
3
4
25.09
˚
and W–N2 bond lengths are identical (2.260 A) and are consistent
with literature values.14,16
10a Ph2PCH2(Ph)2P N(SiMe3)W(CO)4 40.02
=
11b TerpyridineW(CO)4
12c
2,2¢-BiquinolineW(CO)4
13
14
5
6
1234
1260
15d Pyridine-phosphinimineCoCl2
16
17
7
1241
1246
1280
1225
8
18d Pyridine-phosphinimineNiBr2
19d Imidazole-phosphinimineNiBr2
20
21
9
10
1241
1238
a ref. 1a b ref 13. c ref 14 d ref 5.
is observed for the meta-CH3 groups of LXyl. The 31P{ H} NMR
spectra of LOEt and LXyl show singlets at 1.4 and 2.1 ppm and the IR
spectra show characteristic nPN stretches of 1345 and 1328 cm-1.
Although the values are similar for all the proligands, there is
a 32 cm-1 difference between LTol and LXyl which may indicate
conjugation in the molecules affected by slight changes in the
aryl substituent (Table 1, entries 1-4).1a Despite being sterically
unhindered, the newly synthesized proligands have the advantage
of being air and moisture stable (LTol is air and moisture sensitive).
1
Fig. 1 Molecular structure of 3 (depicted with 35% probability ellipsoids,
H atoms are omitted for clarity). Selected bond distances (A) and angles
˚
(◦): P(1)–N(1) = 1.606(5); N(1)–W(1) = 2.260(4); N(2)–W(1) = 2.260(4);
C(23)–W(1) = 1.944(7); C(24)–W(1) = 1.952(6); N(2)–W(1)–N(1) =
76.21(16); N(1)–W(1)–C(23) = 171.3(2); N(2)–W(1)–C(24) = 173.5(2);
C(23)–W(1)–C(24) = 87.6(3).
Cobalt and nickel complexes of LMes and LTol
Tetracarbonyltungsten complexes
The LAr proligands are versatile supports for late transition metals.
Dichlorocobalt(II) complexes, LMesCoCl2 (5) and LTol CoCl2 (6),
were synthesized by the reaction of LMes or LTol with anhydrous
CoCl2 in THF at room temperature and isolated as paramagnetic
air and moisture stable green solids (Scheme 3). The meff for 5
and 6 were measured using a magnetic susceptibility balance
and calculated to be 5.32 mB and 4.26 mB respectively.5 The
nPN stretching frequencies of 5 and 6 are consistent for coordi-
nated phosphinimines (Table 1, entries 13, 14). The molecular
structure of 6 shows a pseudo-tetrahedral geometry with Co–N1
We probed the electronic properties of the LAr proligands by
studying the corresponding tungsten tetracarbonyl complexes.
Complexes LArW(CO)4 (Ar = Mes (1), Tol (2), OEt (3), Xyl
(4)) were synthesized by refluxing a THF solution of the desired
proligand LAr with (THF)W(CO)5 for 18 h and were isolated as
red air and moisture stable solids. The 31P{ H} NMR spectra
1
of 1–4 show a characteristic signal at ~28 ppm indicative of
coordinated phosphinimine. The IR spectra of 1–4 show char-
acteristic ~100 cm-1 decreases in nPN compared to the free ligands
indicating a decrease in the P–N bond order (Table 1, entries 6–
9). There are no significant differences in the nCO values of 1–4,
which are some of the lowest reported for bidentate nitrogen-based
donor ligands on tetracarbonyltungsten(0) moieties (cf . Table 1,
entries 10–12).13,14 This suggests that the LAr ligands exhibit strong
s-donor and unusually poor p-acceptor characteristics.
˚
phosphinimine and Co–N2 imine bond lengths of 2.012(1) A and
˚
2.035(1) A respectively and are comparable to those of a similar
dichlorocobalt(II) complex (Fig. 2).5
Dibromonickel(II) complexes LMesNiBr2 (7) and LTol NiBr2 (8)
were synthesized by reaction of LMes or LTol with Ni(DME)Br2 in
CH2Cl2 at room temperature and were isolated as paramagnetic
air and moisture stable blue solids with meff values of 3.51 and
2.24 mB respectively (Scheme 2).5 The IR spectra of 7 and 8 show
The differences in the steric bulk imparted by the ligands are
clearly seen by comparing the 1H NMR spectra of the respective
542 | Dalton Trans., 2010, 39, 541–547
This journal is
The Royal Society of Chemistry 2010
©

Table 2 Crystallographic data for the X-ray structure determinations of 3, 6, 7, and 10
OEtW(CO)4 (3) Tol CoCl2 (6)
L
L
L
MesNiBr2 (7)
LTol ZnCl2 (10)
empirical formula
fw
C46H39N2O5PCl6W
1127.31
C38H31N2PCl2Co
676.45
C41H37N2PCl2Br2Ni
878.13
C39H33N2PCl4Zn
767.81
T (K)
173
173
173
173
˚
a (A)
12.1621(6)
13.8626(7)
15.8963(13)
101.352(4)
102.052(4)
112.080(3)
2314.0(2)
2
triclinic
P -1
1.618
29.24
55.0
0.483, 0.704
39908
10.935(4)
13.014(3)
13.330(4)
118.200(10)
94.80(2)
95.250(10)
1647.3(8)
2
triclinic
P -1
1.364
7.61
46.8
21.2062(12)
13.2498(7)
13.7667(8)
90
90
90
3868.1(4)
4
orthorhombic
P na21
1.508
12.3640(9)
17.4916(14)
16.9571(13)
90
99.222(3)
90
3619.8(5)
4
monoclinic
P 21/n
1.409
˚
b (A)
˚
c (A)
a (◦)
b (◦)
g (◦)
3
˚
volume (A )
Z
crystal system
space group
dcalc (g/cm3)
m (MoKa) (cm-1)
27.79
55.8
0.642, 0.846
42494
10.49
56.0
0.762, 0.837
42130
2qmax (◦)
absorption correction (Tmin, Tmax
total no. of reflections
)
0.788, 0.846
26521
no. of indep reflections (Rint
)
10320 (0.037)
0.058; 0.126
1.06
7653 (0.039)
0.037; 0.072
1.03
9177 (0.043)
0.044; 0.055
0.98
8741 (0.036)
0.047; 0.081
1.03
residuals (refined on F2, all data): R1; wR2
GOF
no. observations [I > 2s(I)]
residuals (refined on F): R1; wR2
9053
0.047; 0.118
6505
0.028; 0.068
7601
0.029; 0.052
7001
0.031; 0.074
Zinc complexes of LMes and LTol
Previously, we have described the significant effects of ligand
10
sterics on the orthopalladation of LMes and LTol
.
In studying the
analogous zinc complexes we again observe a significant difference
in reactivity based on ligand sterics. The dichlorozinc complexes
Scheme 2
L
MesZnCl2 (9) and LTol ZnCl2 (10) were synthesized by reaction of
LMes or LTol with anhydrous ZnCl2 in THF at room temperature
(Scheme 4). Complex 9 was isolated as an air and moisture stable
1
pale yellow solid with a signature 31P{ H} NMR peak at 29 ppm.
1
Interestingly, the H NMR spectrum of 9 shows only one signal
at 2.02 ppm for the ortho methyl groups on the mesityl moiety
indicating fast rotation at room temperature on the NMR time
scale. As discussed above, in the proligand LMes, tungsten complex
1, and the previously reported palladium analogue we observed
restricted rotation of the aryl group. Likely, in 9 the tetrahedral
geometry of the complex allows for a less hindered system and free
rotation of the mesityl moiety.
Scheme 3
Control of the reaction conditions is very important in obtaining
complex 9 in pure form. Only a minimum amount of THF must
be used to induce the complex to precipitate upon formation.
If the complex remains soluble when stirred overnight at room
characteristic nPN stretching frequencies (Table 1, entries 16, 17).
The molecular structure of 7 shows a slightly distorted tetrahedral
geometry, with identical Ni–N(1) and Ni–N(2) bond lengths
of 1.997(2) A comparable to those of similar phosphinimine
dibromonickel(II) complexes.5
1
temperature, secondary peaks are observed in the 1H and 31P{ H}
NMR spectra of the isolated yellow material.
˚
Synthesis of the tolyl derivative LTol ZnCl2 (10) was carried out
without similar complications to yield air and moisture stable
yellow solid. Complex 10 is insoluble in THF and thus precipitated
1
out of solution upon reaction. The 31P{ H} NMR spectrum of 10
shows a characteristic signal at 27 ppm and the 1H NMR spectrum
shows the tolyl CH3 protons as a singlet at 2.30 ppm. The nPN
of 1238 cm-1 is consistent with other compounds in the series
(Table 1, entry 21). The molecular structure of 10, obtained via
single crystal X-ray crystallography, shows distorted tetrahedral
geometry around the zinc centre (Fig. 2). A comparison of the
structural parameters for 6, 7 and 10 shows no major differences
between the three structures in terms of bond lengths or bond
Scheme 4 In reactions with LMes a saturated solution is required to
form 10
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 541–547 | 543
©

Table 3 Structural details for complexes 6, 7, and 10
6
7
10
˚
Bond lengths (A)
C1–N2
P–N1
M–N1
M–N2
M–X1
M–X2
1.294(2)
1.609(1)
2.012(1)
2.035(1)
2.2289(8)
2.2259(7)
1.286(3)
1.619(2)
1.997(2)
1.997(2)
2.3854(4)
2.3429(4)
1.292(2)
1.6079(14)
2.0212(14)
2.0587(14)
2.2462(5)
2.1929(5)
Bond angles (◦)
N1–M–N2
N1–M–X1
N2–M–X2
X1–M–X2
91.42(5)
89.81(9)
88.04(6)
117.64(4)
108.71(4)
116.35(3)
103.08(5)
113.06(6)
119.40(2)
103.82(4)
117.13(4)
114.83(2)
The dichlorozinc complex LTol ZnCl2 (10) proved to be resistant
to further derivatization. Attempts to form alkoxy, alkyl, or
amido derivatives of 10 were unsuccessful. Reaction of 10 with 2
equiv. NaOEt in THF either at room temperature or at -10 ◦C
1
forms pale yellow solutions with one 31P{ H} NMR signal at
1 ppm, suggesting that the phosphinimine moiety is no longer
coordinated. The 1H NMR spectrum shows peaks in the aromatic
region near 8.2 ppm and characteristic signals for a coordinated
THF molecule are observed at 3.56 and 1.42 ppm. This spectrum
is not consistent with either the free ligand or complex 10 and may
be indicative of dissociation of the phosphinimine moiety while the
imine remains attached. Similar results were observed when only
one equiv. of NaOEt was used. When the reaction was carried out
at room temperature or in refluxing CH2Cl2, CHCl3 or CH3CN the
result was unreacted starting material. Addition of MeMgBr to
complex 10 in THF at -10 ◦C forms a pale yellow solution followed
by formation of a precipitate after the reaction mixture has been
1
stirred at room temperature overnight. The 31P{ H} and 1H NMR
spectra of the solution are consistent with free ligand. Reaction
of complex 10 with 1 equiv. of KN(TMS)2 at -10 ◦C in THF
followed by overnight stirring at room temperature resulted in a
pale yellow solution with the NMR characteristics of a complex
with dissociated phosphinimine moiety and a coordinated imine.
These compounds were not isolable. The reaction of LTol with
Zn(N(TMS)2)2 yielded only free ligand.
Conclusions
We have synthesized a family of bidentate phosphinimine-imine
proligands with different aryl groups on the imine moiety which
can easily be changed to tune the electronic or steric requirements
upon coordination to metal centres. Coordination of the proli-
gands to a tetracarbonyltungsten(0) fragment formed complexes
1–4 which exhibit some of the lowest nCO stretching frequencies
for compounds of this type, suggesting that the LAr system is
Fig. 2 Molecular structures of 6 (top), 7 (middle) and 10 (bottom)
(depicted with 35% probability ellipsoids, H atoms are omitted for clarity).
angles around the metal centre (Table 3). It is worth noting that in
˚
complex 10 the Zn–Cl bond lengths differ by 0.05 A, perhaps due
to amplified steric differences around the smaller zinc centre.
544 | Dalton Trans., 2010, 39, 541–547
This journal is
The Royal Society of Chemistry 2010
©

predominately s-donating with minimal p-acceptor capability.
The differences in steric bulk imparted by the ligand systems was
demonstrated by the hindered rotation around the N–Ar bond for
the bulkier mesityl and xylyl derivatives, 1 and 4.
24 h. Ether was added to the resulting dark yellow solution to
precipitate a bright yellow solid. The solid was filtered and then
dried in vacuo, yielding LOEt as a pale yellow solid, which was
recrystallized from CH2Cl2 (2.25 g, 85%). 1H NMR (300.1 MHz;
We explored the reactivity of the LAr proligands with late
transition metals and showed that, despite the lack of p-acceptor
capability, they were able to form the dichlorocobalt(II) (5, 6),
dibromonickel(II) (7, 8) and the dichlorozinc(II) complexes (9, 10)
via reactions with dihalide metal precursor at room temperature. In
the case of the mesityl derivative 9 the reaction conditions are vital,
as the utilization of too much solvent prevents the product from
precipitating and leads to the formation of impurities. Complex
10 resisted all our attempts at derivatization and was either inert
under the studied reaction conditions, released free ligand, or
formed intractable decomposition products. We can only conclude
that these bulky ligands are not effective in stabilizing neutral
Zn(II) alkoxide, alkyl or amide complexes. Investigations are
currently underway to produce cationic analogues as potential
catalysts for the ring opening polymerization of cyclic esters.
CDCl3): d 1.35 (t, JH-H = 7.0 Hz, 3H, OCH2CH3); 3.91 (q, JH-H =
6 Hz, 2H, OCH2CH3); 6.37 (d, JH-H = 8.4 Hz, 1H, Ar-H); 6.57-
6.49 (m, 5H, Ar-H); 6.92-6.80 (m, 4H, Ar-H); 7.41–7.27 (m,
8H, Ar-H); 7.59–7.46 (m, 8H, Ar-H); 7.90–7.87 (m, 2H, Ar-H).
1
13C{ H} NMR (100.6 MHz; CD2Cl2): d 15.33 (s, OCH2CH3);
63.93 (s, OCH2CH3); 114.40 (s, CH); 116.00 (s, CH); 121.27 (d,
JC-P =10.4 Hz, CH); 122.50 (s, CH); 128.35 (s, CH); 128.87 (s,
CH); 129.00 (s, CH); 129.13 (s, CH); 130.09 (s, CH); 130.88 (s,
C); 131.87 (s, C); 132.21 (d, JC-P = 2.6 Hz, CH); 132.91 (s, CH);
133.00 (s, CH) 141.17 (s, C); 146.16 (s, C); 150.49 (s, C); 155.67
1
(s, C); 170.80 (s, C). 31P{ H} NMR (121.5 MHz; CDCl3): d 1.64
-1
R
(s). IR (Nujolꢀ, cm ): 1622 (nCN), 1345 (nNP). MS (ESI, m/z):
Calc. Mass: 577.2390; Obs. Mass: 577.2409 (M+). Anal. Calcd for
C39H33N2OP (576.67): C, 81.23; H, 5.77; N, 4.86. Found: C, 81.14;
H, 5.77; N, 4.86.
=
(Ph)3PN(C6H4)C(Ph)( N(3,5-Me2C6H4)), LXyl
. The proli-
Experimental
gand LXyl was synthesised in an identical manner to LOEt, except
3,5-dimethylaniline (0.56 g, 4.6 mmol) was used instead of 2,4,6-
trimethylaniline, and the reaction was refluxed for 48 h. The
General procedure
1
reaction yielded LXyl as a yellow solid (2.09 g, 81%). H NMR
Unless otherwise specified all procedures were carried out us-
ing standard Schlenk techniques. A Bruker Avance 300 MHz
spectrometer and Bruker Avance 400dir MHz spectrometer were
(300.1 MHz; CDCl3): d 2.08 (s, 6H, CH3); 6.31 (d, 3JH-H = 6 Hz,
1H, p-NCC6H5); 6.50 (t, 3JH-H = 5.7 Hz, 2H, m-NCC6H5); 6.63 (s,
2H, Ar-H); 6.85–6.77 (m, 2H, Ar-H); 7.37–7.27 (m, 10H, Ar-H);
7.46 (t, JH-H = 5.7 Hz, 3H, Ar-H); 7.57–7.55 (m, 5H, Ar-H); 7.88
used to record the 1H NMR, 13C{ H} NMR, and 31P{ H}
1
1
1
NMR spectra. H NMR chemical shifts are given in ppm versus
(d, JH-H= 6 Hz, 2H, o-NCC6H5). 13C{ H} NMR (100.6 MHz;
CD2Cl2): d 21.63 (s, Ar-m-CH3); 116.82 (s, CH); 118.66 (s, CH);
121.08 (s, CH); 124.93 (s, CH); 128.34 (s, CH); 128.88 (s, CH);
129.01 (s, CH); 129.13 (s, CH); 130.19 (s, CH); 130.86 (s, C); 131.85
(s, C); 132.19 (d, JC-P= 2.7 Hz, CH); 132.91 (s, CH); 133.00 (s, CH);
138.11 (s, C); 140.91 (s, C); 150.39 (s, C); 153.19 (s, C); 170.65 (s, C).
3
1
residual protons in deuterated solvents as follows: d 5.32 for
CD2Cl2, and d 7.27 for CDCl3. 13C{ H} NMR chemical shifts
1
are given in ppm versus residual 13C in solvents as follows: d
54.00 for CD2Cl2, and d 77.23 for CDCl3. 31P{ H} NMR chemical
1
shifts are given in ppm versus 85% H3PO4 set at 0.00 ppm. A
Waters/Micromass LCT mass spectrometer equipped with an
electrospray (ESI) ion source and a Kratos-50 mass spectrometer
equipped with an electron impact ionization (EI) source were used
to record low-resolution and high-resolution spectra. A Nicolet
4700 FT-IR spectrometer was used to record infrared spectra.
Magnetic susceptibility measurements were made with a Johnson
Matthey magnetic susceptibility balance.17 All measurements for
X-ray crystallographic data were made on a Bruker X8 APEX
diffractometer with graphite monochromated Mo-Ka radiation.
31
1
-1
R
P{ H} NMR (121.5 MHz; CDCl3): d 2.18 (s). IR (Nujolꢀ, cm ):
1623 (nCN), 1328 (nNP). MS (ESI, m/z): Calc. Mass: 561.2476;
Obs. Mass: 561.2460 (M+). Anal. Calcd for C39H33N2P (560.67):
C, 83.55; H, 5.93; N, 5.00. Found: C, 83.10; H, 5.89; N, 4.98.
=
(Ph)3PN(C6H4)C(Ph)( N(2,4,6-Me3C6H2))W(CO)4, LMesW-
(CO)4 (1). A solution of tungsten pentacarbonyl (0.20 g,
0.57 mmol) in THF, (15 ml) was added to a suspension of the
proligand LMes (0.18 g, 0.57 mmol) in THF (10 ml). The reaction
mixture was refluxed for 18 h yielding a crimson solution. The
solution was concentrated, and diethyl ether (10 ml) was added to
precipitate a brown solid. Filtration and drying in vacuo yielded
complex 1 as a reddish-brown solid, (0.28 g, 58%). 1H NMR
(300.1 MHz; CD2Cl2): d 1.82 (s, 3H, CH3); 2.17 (s, 3H, CH3);
2.50 (s, 3H, CH3); 6.50 (s, 1H, Ar-H); 6.79–6.59 (m, 3H, Ar-H);
6.88–6.82 (m, 2H, Ar-H); 7.06 (d, JH-H = 9.0 Hz, 2H, Ar-H);
7.33–7.20 (m, 3H, Ar-H); 7.71–7.58 (m, 10H, Ar-H); 7.97–7.90
˚
All solvents were degassed and dried using 3 A molecular sieves
in an mBraun Solvent Purification System. The THF was further
dried over Na and distilled under N2. CD2Cl2 and CDCl3 were
dried over CaH2 and degassed through a series of freeze-pump-
thaw cycles. Ni(DME)Br2 and W(CO)6 were purchased from Strem
Chemicals and used without further purification. W(CO)5THF
was made by the UV photolysis of a THF solution of the desired
amount of W(CO)6 for 4 h. Anhydrous CoCl2,18
were made via literature procedures.10 All other chemicals were
obtained from Aldrich and used without further purification.
LMes, and LTol
(m, 6H, Ar-H). 13C{ H} NMR (100.6 MHz; CD2Cl2): d 19.66 (s,
1
o-CH3); 19.94 (s, o-CH3); 21.00 (s, p-CH3); 120.50 (s, CH); 124.11
(d, JC-P = 10.4 Hz, CH); 126.25 (s, CH); 128.83 (s, CH); 129.33
(s, CH); 129.40 (s, CH); 129.45 (s, CH); 129.78 (s, CH); 130.22
(s, CH); 131.11 (s, CH); 133.65 (d, JC-P = 2.75 Hz, CH); 134.25
(s, C); 134.86 (s, C); 135.51 (s, C); 135.60 (s, C); 138.14 (s, C);
149.36 (s, C); 154.53 (s, C); 173.72 (s, C); 204.46 (s, CO); 204.71 (s,
=
(Ph)3PN(C6H4)C(Ph)( N(4-OEtC6H5)), LOEt
.
A round bot-
tom flask was charged with a spatula head of p-toluidinesulfonic
acid (0.1–0.2 g), 2-(triphenylphosphinimine)benzophenone (2.0 g,
4.6 mmol), p-phenetidine (0.63 g, 4.6 mmol), and toluene (50 mL).
A standard Dean–Stark apparatus topped with a Dryrite drying
column was assembled, and the reaction mixture was refluxed for
CO); 212.07 (s, CO); 215.76 (s, CO). 31P{ H} NMR (121.5 MHz;
1
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 541–547 | 545
©

-1
R
CDCl3): d 27.36 (s). IR (Nujolꢀ, cm ): 1994 (nCO), 1870 (nCO),
1845 (nCO), 1808 (nCO), 1550 (nCN), 1228 (nNP). MS (ESI, m/z):
842.0 ((M - CO)+). Anal. Calcd for C44H35N2O4PW (870.57): C,
60.70; H, 4.05; N, 3.22. Found: C, 61.12; H, 4.24; N, 3.25.
129.55 (s, CH); 130.61 (s, C); 131.47 (s, C); 133.64 (d, JC-P = 2.7 Hz,
CH); 134.09 (s, CH); 134.98 (s, CH); 135.07 (s, CH); 137.89 (s, C);
154.20 (s, C); 154.43 (s, C); 173.91 (s, C); 204.26 (s, CO); 205.89 (s,
1
CO); 214.15 (s, CO); 216.51 (s, CO). 31P{ H} NMR (121.5 MHz;
-1
R
CD2Cl2): d 25.09 (s). IR (Nujolꢀ, cm ): 1998 (nCO), 1874 (nCO),
=
(Ph)3PN(C6H4)C(Ph)( N(4-MeC6H4))W(CO)4, LTol W(CO)4
1842 (nCO), 1808 (nCO), 1549 (nCN), 1241 (nNP). MS (ESI, m/z):
828.1 ((M - CO)+). Anal. Calcd for C43H33N2O4PW.CH2Cl2: C
56.13, H 3.75, N 2.98. Found (%): C 56.04, H 4.00, N 2.96.
(2). Complex 2 was synthesised in an identical manner to
complex 1 using the proligand LTol (0.31 g, 0.57 mmol) instead.
Complex 2 was isolated as a brown solid, (0.34 g, 70%). 1H NMR
(300.1 MHz; CD2Cl2): d 2.23 (s, 3H, CH3); 6.68–6.65 (m, 4H,
=
(Ph)3PN(C6H4)C(Ph)( N(2,4,6-Me3C6H2))CoCl2, LMesCoCl2
Ar-H); 6.77 (dt, JH-H= 8.4, 1.8 Hz, 2H, Ar-H); 6.90 (td, JH-H
=
(5). A Schlenk flask was loaded with proligand LMes (0.5 g,
0.87 mmol) and anhydrous CoCl2 (0.12 g, 0.96 mmol), and THF
(20 ml) was added. The reaction mixture was stirred for 18 h at
room temperature, which resulted in the formation of a green
suspension. Ether (20 ml) was added to further precipitate the
8.7 Hz, 1.8, 2H, Ar-H); 7.28–7.04 (m, 7H, Ar-H); 7.69–7.55 (m,
8H, Ar-H); 7.97–7.90 (m, 5H, Ar-H). 13C{ H} NMR (100.6 MHz;
1
CD2Cl2): d 21.13 (s, CH3); 120.93 (s, CH); 124.05 (d, JC-P
=
10.7 Hz, CH); 126.37 (s, C); 127.37 (s, C); 128.25 (s, CH); 129.00
(s, CH); 129.38 (s, CH); 129.46 (s, CH); 129.59 (s, CH); 130.72 (s,
CH); 131.53 (s, CH); 133.66 (d, JC-P = 2.7 Hz, CH); 134.18 (s,
C); 134.99 (s, CH); 135.08 (s, CH); 138.05 (s, C); 152.27 (s, C);
154.51 (s, C); 174.44 (s, C); 204.23 (s, CO); 205.79 (s, CO); 214.18
green solid, and after filtration, washing with ether (3 ¥ 5 ml) and
-1
R
drying under vacuum yielded 5 (0.47 g, 76%). IR (Nujolꢀ, cm ):
1553 (nCN), 1238 (nNP). meff = 5.32 mB. MS (EI, m/z): Calc. Mass:
703.1260; Obs. Mass: 703.1247 (M); Calc. Mass: 667.1461; Obs.
Mass: 667.1480 (M - HCl). Anal. Calcd for C40H35N2PCl2Co
(704.53): C, 68.19; H, 5.01; N, 3.98. Found: C, 68.27; H, 4.97; N,
3.97.
(s, CO); 216.46 (s, CO). 31P{ H} NMR (121.5 MHz; CD2Cl2): d
1
-1
R
25.34 (s). IR (Nujolꢀ, cm ): 1996 (nCO), 1870 (nCO), 1846 (nCO),
1805 (nCO), 1553 (nCN), 1242 (nNP). MS (ESI, m/z): 814.2 ((M -
CO)+). We were not able to purify this compound.19
=
(Ph)3PN(C6H4)C(Ph)( N(4-MeC6H4))CoCl2, LTol CoCl2 (6).
=
(Ph)3PN(C6H4)C(Ph)( N(4-OEtC6H4))W(CO)4, LOEtW(CO)4
Complex 6 was made in an identical manner to 5, using proligand
(3). Complex 3 was synthesised in an identical manner to
complex 1 using the proligand LOEt (0.18 g, 0.57 mmol) instead.
Complex 3 was isolated as a light reddish-brown solid, and was
L
Tol (0.5 mg, 0.91 mmol), and CoCl2 (0.13 g, 1.01 mmol). Yielding
a green solid of 6 (0.46 g, 74%). A single crystal suitable for X-
ray crystallography was grown from cooling a solution of DCM
1
-1
recystralised from DCM and hexane, (0.33 g, 66%). H NMR
R
and hexane. IR (Nujolꢀ, cm ): 1547 (nCN), 1234 (nNP). meff
=
(300.1 MHz; CD2Cl2): d 1.33 (t, JH-H = 5.4 Hz, 3H, OCH2CH3);
4.26 mB. MS (EI, m/z): Calc. Mass: 675.0924; Obs. Mass: 675.0934
(M); Calc. Mass: 640.1252; Obs. Mass: 640.1245 (M - Cl). Anal.
Calcd for C38H31N2PCl2Co (676.48): C, 67.47; H, 4.62; N, 4.14.
Found: C, 67.47; H, 4.73; N, 4.01.
3.93 (q, JH-H = 5.4 Hz, 2H, OCH2CH3); 6.68–6.61 (m, 3H, Ar-
H); 6.774 (dt, JH-H = 6.0, 1.5 Hz, 2H, Ar-H); 6.91 (dt, JH-H
=
5.7, 1.5 Hz, 2H, Ar-H); 7.05 (dd, JH-H = 6.0, 1.2 Hz, 2H, Ar-
H); 7.29–7.22 (m, 4H, Ar-H); 7.68–7.56 (m, 9H, Ar-H); 7.95-7.90
(m, 6H, Ar-H). 13C{ H} NMR (100.6 MHz; CD2Cl2): d 15.17 (s,
1
=
(Ph)3PN(C6H4)C(Ph)( N(2,4,6-Me3C6H2))NiBr2, LMesNiBr2
(7). A yellow solution of proligand LMes (0.5 g, 0.87 mmol)
in DCM (10 ml) was added to a suspension of Ni(DME)Br2
(0.3 g, 0.96 mmol) in DCM (10 ml). The reaction mixture
immediately turns green and was stirred at room temperature
for 18 h. The resulting dark green solution was concentrated in
vacuo and ether (20 ml) was added to precipitate a blue solid.
Filtration, washing with ether (3 ¥ 5 ml), and drying under
vacuum yielded a blue solid of 7 (0.49 g, 71%). A single crystal
OCH2CH3); 64.08 (s, OCH2CH3); 120.94 (s, CH); 124.02 (d, JC-P
=
9.3 Hz, CH); 126.37 (s, C); 127.38 (s, C); 128.31 (s, CH); 129.40
(s, CH); 129.47 (s, CH); 129.60 (s, CH); 130.80 (s, C); 131.53 (s,
C); 133.67 (d, JC-P= 2.6 Hz, CH); 134.15 (s, CH); 134.98 (s, CH);
135.08 (s, CH); 138.18 (s, C); 148.43 (s, C); 154.54 (s, C); 156.56 (s,
C); 174.61 (s, C); 204.12 (s, CO); 205.88 (s, CO); 214.36 (s, CO);
216.46 (s, CO). 31P{ H} NMR (121.5 MHz; CDCl3): d 28.60 (s).
1
-1
R
IR (Nujolꢀ, cm ): 1995 (nCO), 1879 (nCO), 1852 (nCO), 1802 (nCO),
suitable for X-ray crystallography was grown from slow cooling
1533 (nCN), 1231 (nNP). MS (ESI, m/z): Calc. Mass: 844.1659; Obs.
Mass: 844.1687 ((M - CO)+). Anal. Calcd for C43H33N2O5PW
(872.55): C, 59.19; H, 3.81; N, 3.21. Found: C, 58.43; H, 3.85; N,
3.19.
-1
R
a solution of DCM and hexane. IR (Nujolꢀ, cm ): 1558 (nCN),
1242 (nNP). meff = 3.51 mB. MS (EI, m/z): Calc. Mass: 713.1042;
Obs. Mass: 713.1054 for C40H35N2P58Ni81Br and 713.1029 for
C40H35N2P60Ni79Br (M - Br). Calc. Mass: 711.1093; Obs. Mass:
711.1075 for C40H35N2P58Ni79Br (M - Br). Anal. Calcd for
C40H35N2PBr2Ni (793.20): C, 60.57; H, 4.45; N, 3.53. Found: C,
60.48; H, 4.45; N, 3.51.
=
(Ph)3PN(C6H4)C(Ph)(
N(3,5 - Me2C6H3))W(CO)4, LXylW -
(CO)4 (4). Complex 4 was synthesised in an identical manner to
complex 1 using the proligand LXyl (0.18 g, 0.57 mmol) instead.
Complex 4 was isolated as a light brown solid, (0.30 g, 62%).
1H NMR (300.1 MHz; CD2Cl2): d 2.06 (s, 3H, CH3); 2.29 (s, 3H,
=
(Ph)3PN(C6H4)C(Ph)( N(4-MeC6H4))NiBr2, LTol NiBr2 (8).
CH3); 6.05 (s, 1H, Ar-H); 6.67–6.59 (m, 3H, Ar-H); 6.78 (dt, JH-H
=
Complex 8 was made in an identical manner to 7, using proligand
6.3, 1.8 Hz, 1H, Ar-H); 6.90 (td, JH-H= 7.5, 1.8 Hz, 1H, Ar-H); 7.01
LTol (0.5 g, 0.91 mmol), and Ni(DME)Br2 (0.31 g, 1.01 mmol).
-1
R
(s, 1H, Ar-H); 7.11–7.08 (m, 2H, Ar-H); 7.28–7.23 (m, 3H, Ar-H);
Yielding a blue solid of 8 (0.48 g, 69%). IR (Nujolꢀ, cm ):
7.69-7.55 (m, 9H, Ar-H); 7.97–7.90 (m, 6H, Ar-H). 13C{ H} NMR
1548 (nCN), 1247 (nNP). meff = 2.24 mB. MS (EI, m/z): Calc.
Mass: 685.0742; Obs. Mass: 685.0741 for C38H31N2P58Ni81Br, and
685.0716 for C38H31N2P60Ni79Br (M - Br). Calc. Mass: 683.077;
Obs. Mass: 683.0762 for C38H31N2P58Ni79Br (M - Br). Anal. Calcd
1
(100.6 MHz; CD2Cl2): d 21.57 (s, m-CH3); 31.15 (s, m-CH3); 119.47
(s, CH); 120.94 (s, CH); 124.08 (d, JC-P = 9.2 Hz, CH); 126.37 (s,
CH); 126.74 (s, CH); 127.38 (s, C); 128.17 (s, CH); 129.43 (s, CH);
546 | Dalton Trans., 2010, 39, 541–547
This journal is
The Royal Society of Chemistry 2010
©

for C38H31N2PBr2Ni (765.15): C, 63.89; H, 4.69; N, 3.73. Found:
C, 64.12; H, 4.78; N, 3.72.
Notes and references
1 (a) K. V. Katti and R. G. Cavell, Organometallics, 1989, 8, 2147; (b) P. G.
Hayes, G. C. Welch, D. J. H. Emslie, C. L. Noack, W. E. Piers and M.
Parvez, Organometallics, 2003, 22, 1577; (c) B. Liu, D. Cui, J. Ma, X.
Chen and X. Jing, Chem.–Eur. J., 2007, 13, 834; (d) K. D. Conroy, W. E.
Piers and M Parvez, J. Organomet. Chem., 2008, 693, 834.
2 (a) T. T. Co, S. C. Shim, C. S. Cho and T.-J. Kim, Organometallics, 2005,
24, 4824; (b) C. Metallinos, D. Tremblay, F. B. Barrett and N. J. Taylor,
J. Organomet. Chem., 2006, 691, 2044; (c) M. Sauthier, J. Fornies-
Camer, L. Toupet and R. Reau, Organometallics, 2000, 19, 553; (d) L.
Beaufort, A. Demonceau and A. F. Noels, Tetrahedron, 2005, 61, 9025;
(e) M. Sauthier, F. Leca, R. F. de Souza, K. Bernardo-Gusmao, L. F. T.
Queiroz, L. Toupet and R. Reau, New J. Chem., 2002, 26, 630; (f) K.
Bernardo-Gusmao, L. F. T. Queiroz, R. F. de Souza, F. Leca, C. Loup
and R. Reau, J. Catal., 2003, 219, 59.
3 (a) K. Dehnicke and F. Weller, Coord. Chem. Rev., 1997, 158, 103;
(b) S. A. Bell, T. Y. Meyer and S. J. Geib, J. Am. Chem. Soc., 2002,
124, 10698; (c) M. C. Burland and T. Y. Meyer, Inorg. Chem., 2003,
42, 3438; (d) G. C. Welch, W. E. Piers, M. Parvez and R. McDonald,
Organometallics, 2004, 23, 1811; (e) S. Hawkeswood and D. W. Stephan,
Dalton Trans., 2005, 2182; (f) S. Hawkeswood, P. Wei, J. W. Gauld and
D. W. Stephan, Inorg. Chem., 2005, 44, 4301; (g) S. Courtenay, D. Walsh,
S. Hawkeswood, P. Wei, A. K. Das and D. W. Stephan, Inorg. Chem.,
2007, 46, 3623.
4 (a) K. Aparna, R. P. K. Babu, R. McDonald and R. G. Cavell, Angew.
Chem., Int. Ed., 2001, 40, 4400; (b) R. P. K. Babu, R. McDonald and
R. G. Cavell, Chem. Commun., 2000, 481; (c) A. Kasani, R. P. K. Babu,
R. McDonald and R. G. Cavell, Angew. Chem., Int. Ed., 1999, 38, 1483;
(d) A. Kasani, R. McDonald and R. G. Cavell, Chem. Commun., 1999,
1993.
5 L. P. Spencer, R. Altwer, P. Wei, L. Gelmini, J. Gauld and D. W. Stephan,
Organometallics, 2003, 22, 3841.
6 H-R. Wu, Y-H. Liu, S-M. Peng and S-T. Liu, Eur. J. Inorg. Chem.,
2003, 3152.
=
(Ph)3PN(C6H4)C(Ph)( N(2,4,6-Me3C6H2))ZnCl2, LMesZnCl2
(9). A Schlenk flask was loaded with proligand 1a (0.5 g, 0.87
mmol) and anhydrous ZnCl2 (0.13 g, 0.96 mmol), and THF
(5 ml) was added. The reaction mixture was stirred for 18 h at
room temperature, which resulted in the formation of a yellow
suspension. After filtration, washing with hexanes (3 ¥ 5 ml) and
drying under vacuum 9 was isolated as a pale yellow solid, (0.53 g,
86%). 1H NMR (400.2 MHz; CD2Cl2): d 2.02 (s, 6H, o-CH3); 2.18
(s, 3H, p-CH3); 6.68 (m, 3H, Ar-H); 6.75 (t, JH-H= 8.0 Hz, 1H,
Ar-H); 6.91 (m, 2H, Ar-H); 7.08 (d, JH-H = 4.0 Hz, 2H, Ar-H);
7.26 (t, JH-H = 8.0 Hz, 2H, Ar-H); 7.36 (t, JH-H = 8.0 Hz, 1H,
Ar-H); 7.57 (dt, dJH-H = 4.0 Hz, tJH-H = 8.0 Hz, 6H, Ar-H); 7.68
(t, JH-H = 8.0 Hz, 3H, Ar-H); 7.88 (q, JH-H= 8.0 Hz, 6H, Ar-H).
13C NMR (100.6 MHz; CD2Cl2): d 19.42 (s, o-CH3); 21.07 (s,
p-CH3); 121.06 (s, CH); 125.53 (d, C); 126.53 (s, C); 127.23 (d,
JC-P= 11.1 Hz, CH); 128.23 (s, CH); 129.03 (s, CH); 129.54 (s, C);
129.63 (s, CH); 129.78 (d, JC-P = 5.0 Hz, CH); 130.70 (s, CH);
131.86 (CH); 133.97 (d, JC-P = 3.0 Hz, CH); 134.79 (d, JC-P
=
11.1 Hz, CH); 135.15 (s, CH); 135.58 (s, C); 137.95 (s, C); 143.08
(s, C); 150.05 (s, C); 175.95 (s, C). 31P NMR (161.2 MHz; CD2Cl2):
-1
R
d 29.87 (s). IR (Nujolꢀ, cm ): 1556 (nCN), 1241 (nNP). MS (EI,
m/z): 673.0 (M - Cl)+. Anal. Calcd for C40H35N2PCl2Zn (710.86):
C, 67.57; H, 4.69; N, 3.94. Found: C, 67.49; H, 4.88; N, 4.05.
=
(Ph)3PN(C6H4)C(Ph)( N(4-MeC6H4))ZnCl2, LTol ZnCl2 (10).
A Schlenk flask was loaded with proligand LTol (0.48 g,
0.87 mmol) and anhydrous ZnCl2 (0.13 g, 0.96 mmol), and THF
(10 ml) was added. The reaction mixture was stirred for 18 h at
room temperature, which resulted in the formation of a yellow
suspension. Ether (10 ml) was added to further precipitate the
yellow solid, and after filtration, washing with ether (3 ¥ 5 ml)
and drying under vacuum yielded 10 as a yellow solid (0.53 g,
89%). 1H NMR (400.2 MHz; CD2Cl2): d 2.30 (s, 3H, pTol-CH3);
6.55 (d, JH-H = 8.0 Hz, 1H, Ar-H); 6.76 (t, JH-H = 8.0 Hz, 1H,
Ar-H); 6.86 (t, JH-H = 8.0 Hz, 3H, Ar-H); 6.95 (t, JH-H = 8.0 Hz,
7 S. Al-Benna, M. J. Sarsfield, M. Thorton-Pett, D. L. Ormsby, P. J.
Maddox, P. Bres and M. Bochmann, J. Chem. Soc., Dalton Trans.,
2000, 4247.
8 D. W. Stephan, Organometallics, 2005, 24, 2548.
9 (a) D. Aguilar, R. Bielsa, M. Contel, A. Lledos, R. Navarro, T. Soler
and E. P. Urriolabeitia, Organometallics, 2008, 27, 2929; (b) R. Bielsa,
R. Navarro, T. Soler and E. P. Urriolabeitia, Dalton Trans., 2008, 1203;
(c) R. Bielsa, A. Larrea, R. Navarro, T. Soler and E. P. Urriolabeitia,
Eur. J. Inorg. Chem., 2005, 1724.
10 C. J. Wallis, I. L. Kraft, J. N. Murphy, B. O. Patrick and P.
Mehrkhodavandi, Organometallics, 2009, 28, 3889.
11 (a) A. F. Douglas, B. O. Patrick and P. Mehrkhodavandi, Angew. Chem.,
Int. Ed., 2008, 47, 2290; (b) G. Labourdette, D. J. Lee, B. O. Patrick,
M. B. Ezhova and P. Mehrkhodavandi, Organometallics, 2009, 28, 1309.
12 (a) M. D. Hannant, M. Schormann and M. Bochmann, J. Chem. Soc.,
Dalton Trans., 2002, 4071; (b) M. D. Hannant, M. Schormann, D. L.
Hughes and M. Bochmann, Inorg. Chim. Acta, 2005, 358, 1683; (c) C. A.
Wheaton, B. J. Ireland and P. G. Hayes, Organometallics, 2009, 28, 1282;
(d) C. A. Wheaton, P. G. Hayes and B. J. Ireland, Dalton Trans., 2009,
4832.
13 S. A. Moya, R. Pastene, H. Le Bozec, P. J. Baricelli, A. J. Pardy and J.
Gimeno, Inorg. Chim. Acta, 2001, 312, 7.
14 A. O. Youssef, M. M. H. Khalil, R. M. Ramadan and A. A. Soliman,
Transition Met. Chem., 2003, 28, 331.
1H, Ar-H); 7.02 (d, JH-H = 4.0 Hz, 2H, Ar-H); 7.08 (d, JH-H
=
8.0 Hz, 2H, Ar-H); 7.27 (t, JH-H = 8.0 Hz, 2H, Ar-H); 7.36 (t,
JH-H = 8.0 Hz, 1H, Ar-H); 7.52 (t, JH-H = 8.0 Hz, 6H, Ar-H); 7.65
(t, JH-H = 4.0 Hz, 3H, Ar-H); 7.79 (dd, JH-H = 8.0, 4.0 Hz, 6H,
1
Ar-H). 13C{ H} NMR (100.6 MHz; CD2Cl2): d 21.34 (s, CH3);
121.82 (s, CH); 124.02 (s, CH); 126.11 (s, C); 127.11 (s, C); 128.29
(d, JC-P = 8.1 Hz, CH); 128.63 (s, CH); 129.70 (t, JC-P = 13.1 Hz,
CH); 130.28 (s, CH); 130.51 (s, CH); 132.14 (s, CH); 133.91 (d,
JC-P = 3.0 Hz, CH); 134.31 (s, CH); 134.41 (s, CH); 134.82 (s,
CH); 136.36 (s, C); 137.26 (s, C); 144.64 (s, C); 148.60 (s, C);
15 The material crystallized with three molecules of CH2Cl2 in the
asymmetric unit. Two of these solvent molecules are disordered and
were modelled in two orientations.
1
176.10 (s, C). 31P{ H} NMR (162.0 MHz; CD2Cl2): d 27.52 (s).
-1
R
IR (Nujolꢀ, cm ): 1551 (nCN), 1238 (nNP). MS (Maldi-TOF,
16 (a) K. V. Katti, B. D. Santarsiero, A. A. Pinkerton and R. G. Cavell,
Inorg. Chem., 1993, 32, 5919; (b) E. Subasi, H. Temel, O. S. Senturk
and F. Ugur, J. Coord. Chem., 2006, 59, 1807; (c) Q. Ye, Q. Wu, H.
Zhao, Y.-M. Song, X. Xue, R.-G. Xiong, S.-M. Pang and G.-H. Lee,
J. Organomet. Chem., 2005, 690, 286.
m/z): 645.2 (M - Cl)+. Anal. Calcd for C38H31N2PCl2Zn·CH2Cl2
(767.61): C, 61.87; H, 4.69; N, 3.52. Found: C, 61.59; H, 4.43;
N, 3.51.
17 G.A. Miessler and D. A. Tarr, Inorganic Chemistry, 2nd Edn, Prentice
Acknowledgements
Hall, New Jersey, 1998, pp. 313–316.
18 J-H. So and P. Boudjouk, Inorg. Chem., 1990, 29, 1592.
19 Complex 3 was highly soluble in a variety of solvents which prevented
its purification in the bulk state.
The authors would like thank UBC and NSERC of Canada for
funding and Mr. J. N. Murphy for preparation of some ligands.
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 541–547 | 547
©