Half-sandwich ruthenium(II) complexes of aminophosphines: Synthesis, structures and catalytic applications in C-C coupling reactions between styrenes and diphenyldiazomethane

Article abstract of DOI:10.1016/j.jorganchem.2003.09.020

The half-sandwich Ru(II) complexes of the type [CpRu(PPh₂ N(H)R)(PPh₃)Cl], [CpRu(PPh₂N(H)R)₂Cl] (R=Ph, C₆H₁₁) and [CpRu(PPh₂N(R′) PPh₂-κP,κP)(PPh₃)]Cl (R′=Et, ⁿPr, ⁱPr, ⁿBu), were synthesized and the structures of complexes [CpRu(PPh₂N(H)Ph)(PPh₃) Cl] and [CpRu(PPh₂N(H)Ph)₂Cl] were confirmed by single crystal X-ray diffraction studies. All ruthenium complexes were employed in the cyclopropanation reaction of styrene derivatives in the presence of diphenyldiazomethane. All complexes afford 1,1,3,3-tetraphenyl cyclobutane along with cyclopropane derivatives; complex, [CpRu(PPh₂N(ⁿBu)PPh₂-κ P,κP) (PPh₃)]Cl shows better selectivity in the formation of 1,1,2-triphenylcyclopropane. In all reactions appreciable amounts of cyclopropanation products and metathesis products, 1,2-diphenylcyclopropane and 1,1-diphenylethene were obtained along with 1,1,3-triphenylpropene derivatives. The variable temperature NMR studies have suggested that the cyclopropanation reactions in the presence of ionic complex, [CpRu(PPh₂N(R′)PPh ₂-κP,κP)(PPh₃)]Cl proceeds via carbene intermediate, [CpRu(=CPh₂)(PPh₂N(R′) PPh₂-κP)(PPh₃)]Cl.

Full text of DOI:10.1016/j.jorganchem.2003.09.020

Journal of Organometallic Chemistry 688 (2003) 227ꢀ235
/
www.elsevier.com/locate/jorganchem
Half-sandwich ruthenium(II) complexes of aminophosphines:
synthesis, structures and catalytic applications in CꢀC coupling
reactions between styrenes and diphenyldiazomethane
/
Srinivasan Priya a, Maravanji S. Balakrishna a,*, Shaikh M. Mobin b,
Robert McDonald c
a Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076, India
b National Single Crystal X-ray Diffraction Facility, Indian Institute of Technology, Bombay, Mumbai 400 076, India
c X-ray Diffraction Facility, University of Alberta, Edmonton, Canada T6G 2G2
Received 11 August 2003; received in revised form 4 September 2003; accepted 4 September 2003
Abstract
The half-sandwich Ru(II) complexes of the type [CpRu(PPh2N(H)R)(PPh3)Cl], [CpRu(PPh2N(H)R)2Cl] (Rꢁ
/
Ph, C6H11) and
Et, nPr, i Pr, nBu), were synthesized and the structures of complexes
[CpRu(PPh2N(R?)PPh2-kP,kP)(PPh3)]Cl (R?ꢁ
/
[CpRu(PPh2N(H)Ph)(PPh3)Cl] and [CpRu(PPh2N(H)Ph)2Cl] were confirmed by single crystal X-ray diffraction studies. All
ruthenium complexes were employed in the cyclopropanation reaction of styrene derivatives in the presence of diphenyldiazo-
methane. All complexes afford 1,1,3,3-tetraphenyl cyclobutane along with cyclopropane derivatives; complex, [CpRu(PPh2N(n-
Bu)PPh2-kP,kP)(PPh3)]Cl shows better selectivity in the formation of 1,1,2-triphenylcyclopropane. In all reactions appreciable
amounts of cyclopropanation products and metathesis products, 1,2-diphenylcyclopropane and 1,1-diphenylethene were obtained
along with 1,1,3-triphenylpropene derivatives. The variable temperature NMR studies have suggested that the cyclopropanation
reactions in the presence of ionic complex, [CpRu(PPh2N(R?)PPh2-kP,kP)(PPh3)]Cl proceeds via carbene intermediate, [CpRu(ꢀ
/
CPh2)(PPh2N(R?)PPh2-kP)(PPh3)]Cl.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Aminophosphine; Ruthenium(II) complexes; Cyclopropanation; Crystal structures
1. Introduction
tion in classical catalytic processes such as
hydrogenation [4], isomerisation [5,6], decarbonylation
[7ꢀ9], reductive elimination [10], oxidative addition [11],
in making and breaking CꢁH bonds [12], and cleavage
of NꢁH and OꢁH bonds [13]. In recent years ruthenium
complexes of phosphines are utilized in the catalytic
cyclopropanation reactions and the popular Grubbs
catalyst [14] comes under this category. The factors
governing the activity and mechanism for the cyclopro-
panation are not known. However, the half-sandwich
ruthenium complexes of the type [CpRu(PR3)2X] have
been proven to be effective catalysts for dimerisation of
ethyldiazoacetate [15,16]. Thus, as a part of our ongoing
research [17], we have examined the catalytic activity of
the reactions of terminal olefins with diazo compound
In recent years, there has been an exponential increase
in the use of transition metal complexes containing
phosphines in organic transformations [1,2]. Among
different types of transition metal complexes known, the
rhodium complexes play prominent role in terms of
highest efficiency and the turnover number [3]. Ruthe-
nium has been introduced as a cheaper alternative to the
rhodium, however, the limitation associated with it is its
low turnover numbers. Ruthenium complexes of phos-
phines are of considerable interest as they find applica-
/
/
/
/
* Corresponding author. Fax: ꢂ91-22-2576-7152.
E-mail address: krishna@iitb.ac.in (M.S. Balakrishna).
/
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.09.020

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S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ235
/
using Ru(II) complexes of aminophosphines; the pre-
liminary results are presented. To the best of our
knowledge this is the first instance where the complexes
of aminophosphines are employed in this type of
catalytic reaction.
2. Results and discussion
The reactions of aminophosphines, Ph2PN(H)R (Rꢁ
/
Ph, 1; C6H11, 2) with CpRuCl(PPh3)2] afford monosub-
stituted [CpRuCl(PPh3)(PPh2N(H)R)] or disubstituted
[CpRuCl(PPh2N(H)R)2] complexes depending upon the
stoichiometry and the reaction conditions. The reactions
Fig. 1. Perspective view of [CpRuCl(PPh3)(PPh2N(H)Ph)] (3) showing
50% probability thermal ellipsoids.
of Ph2PN(H)R (RꢁPh, 1; C6H11, 2) with
/
[CpRuCl(PPh3)2] in dichloromethane in equimolar ratio
at room temperature, afford [CpRuCl(PPh3)(PPh2-
described as pseudo octahedral three-legged piano stool.
˚
N bond distance(s) of 1.681(3) A in 3 and
˚
1.688(3) and 1.700(3) A in 4 are slightly shorter than the
N(H)R)] (Rꢁ
Ph, 3; C6H11, 5) in good yield. The 31P-
/
The Pꢁ
/
NMR spectra of complexes 3 and 5 show two doublets
at 42.9, 72.4 ppm and 42.9, 77.9 ppm, respectively. The
chemical shifts at high fields are due to the PPh3 group
whereas the aminophosphines appear at lower field. The
2JPRuP couplings are 42.4 and 48.5 Hz for complexes 3
and 5, respectively. The reactions of [CpRuCl(PPh3)2]
˚
sum of Pauling covalent radii (1.77 A) as expected due
to the Pꢁ
/
N multiple bonding. The Ruꢁ
/
P(1) and Ruꢁ
/
˚
˚
P(2) distances (2.289(2) A and 2.309(1) A in 3 and
˚
2.290(1) A and 2.302(1) A in 4) are comparable with
˚
˚
those in [CpRu(PPh3)2Cl] [18] (2.337(1) and 2.225(1) A),
˚
[CpRu(PMe3)2Cl] [18] (2.373(5) and 2.280(6) A) and are
with 1 and 2 in 1:2 molar ratio in toluene at 80ꢀ
resulted in the formation of disubstituted complexes of
the type, [CpRuCl(PPh2N(H)R)2] (RꢁPh, 4; C6H11, 6)
in Â75% yield containing trace amount of monosub-
stituted complex, [CpRuCl(PPh3)(PPh2N(H)R)] (Rꢁ
/
90 8C
shorter when compared to [CpRu{P(OMe)3}2Cl] [19]
˚
/
(2.234(2) and 2.199(3) A). The C?ꢁ
/
RuꢁCl (C? is the
/
/
centroid of the C5H5 ring) angle is smaller when
compared to other C?ꢁRuꢁP(1) and C?ꢁRuꢁP(2) angles
and the P(1)ꢁRuꢁP(2) angles are wider when compared
to PꢁRuꢁCl angles in both 3 and 4.
The reactions of aminobis(phosphines), Ph2PN(R)-
PPh2 (Rꢁ
Et, nPr, iPr, nBu) with equimolar quantity of
[CpRuCl(PPh3)2] afford cationic complexes, [CpRu-
(PPh3)(Ph2PN(R)PPh2-kP,kP)]Cl (Rꢁ
Et [20], 7; nPr,
8; iPr, 9; nBu, 10) in 50ꢀ60% yield (Scheme 2). The 31P-
NMR spectra of complexes 7ꢀ10 show triplets for PPh3
around 44ꢀ45 ppm and doublets for PPh2 in the range
of 80ꢀ83 ppm with JPRuP couplings of 35 Hz. Further
/
/
/
/
/
Ph, 3; C6H11, 5). The 31P-NMR spectra of complexes
4 and 6 show single resonances at 72.6 and 81.8 ppm,
respectively. The monosubstituted complex 3 with
excess of ligand 1 also affords the disubstituted complex
4 as shown in Scheme 1. The structures of complexes 3
and 4 are established by single crystal X-ray diffraction
studies.
/
/
/
/
/
/
/
The perspective views of complexes 3 and 4 are shown
in Figs. 1 and 2 respectively. Crystallographic data,
selected bond distances and bond angles are given in
/
/
2
/
Tables 1ꢀ3. The coordination geometry around ruthe-
/
evidence for the formation of complexes 7ꢀ10 comes
/
nium centres in both complexes 3 and 4 may be
from the 1H-NMR spectra and the microanalytical data.
2.1. Cyclopropanation of styrenes with Ph2CN2 using
half sandwich Ru(II) catalysts
Diphenyldiazomethane on treatment with styrene
gives 1,1,2-triphenyl propane under thermal or photo-
chemical conditions by the elimination of N2 [21].
Baratta et al. [15] have reported that the presence of a
catalytic amount of [CpRuCl(PPh3)2] in the above
reaction leads to a mixture of products as shown in
Eq. (1) with 1,1,2-triphenyl propane as the minor
product.
Scheme 1.

S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ
/
235
229
Fig. 2. Perspective view of [CpRuCl(PPh2N(H)Ph)2] (4) showing 50% probability thermal ellipsoids.
Table 1
Crystallographic data for complexes 3 and 4
Table 2
˚
Selected bond distances (A) and bond angles (8) for 3
3
4
Bond distances
Ruꢁ
Ruꢁ
Ruꢁ
Ruꢁ
P(1)ꢁ
P(1)ꢁ
P(2)ꢁ
N(1)ꢁ
/
Cl
2.437(1)
2.309(1)
2.196(3)
2.217(3)
1.680(3)
1.824(3)
1.851(3)
1.372(4)
Ruꢁ
Ruꢁ
Ruꢁ
Ruꢁ
P(1)ꢁ
P(2)ꢁ
P(2)ꢁ
/
P(1)
C(1)
C(3)
C(5)
2.289(1)
2.214(3)
2.192(3)
2.214(3)
1.838(3)
1.843(3)
1.829(3)
Empirical formula
Formula weight
Crystal system
Space group
C
741.17
41H36ClNP2Ru
C41H37ClN2P2Ru
756.19
/
P(2)
C(2)
C(4)
/
/
/
Monoclinic
P21/n (No. 14)
13.0280(10)
16.5916(12)
16.4422(12)
Monoclinic
P21 (No.4)
10.1530(6)
18.1520(7)
10.5140(11)
/
/
/N(1)
/
C(11)
C(51)
C(61)
˚
a (A)
/C(21)
/
˚
b (A)
/C(41)
/
˚
c (A)
/C(31)
a (8)
b (8)
g (8)
V (A )
Z
Dcalc (g cmꢃ1
ꢀ/
ꢀ/
Bond angles
ClꢁRuꢁP(1)
P(1)ꢁRuꢁ
RuꢁP(1)ꢁ
N(1)ꢁ
N(1)ꢁ
RuꢁP(2)ꢁ
RuꢁP(2)ꢁ
C(41)ꢁ
C?ꢁRuꢁ
C?ꢁRuꢁ
104.676(1)
113.825(6)
/
/
89.50(3)
Clꢁ
/
Ruꢁ
P(1)ꢁ
P(1)ꢁ
104.01(15) C(11)ꢁP(1)ꢁ
105.78(14) RuꢁP(2)ꢁC(51)
108.50(10) C(41)ꢁP(2)ꢁ
118.00(10) C(51)ꢁP(2)ꢁ
102.74(16) P(1)ꢁN(1)ꢁ
RuꢁC(1)
/
P(2)
C(11)
N(1)
C(21)
89.36(3)
113.98(10)
111.69(10)
104.01(14)
120.98(11)
103.50(14)
100.86(14)
131.4(2)
ꢀ/
ꢀ/
/
/
P(2)
96.90(3)
Ruꢁ
/
/
3
˚
3438.1(4)
4
1772.6(2)
2
/
/C(21)
116.25(11) Ruꢁ
/
/
/
P(1)ꢁ
/
C(11)
C(21)
/
/
)
1.432
0.658
193
1.417
0.640
293
/
P(1)ꢁ
/
/
/
m(Moꢀ )
Ka) a (mmꢃ1
Temperature (K)
/
/
/C(41)
/
/
C(51)
C(61)
/
/C(61)
/
/
b
R
Rw
0.0377
0.0811
0.0187
0.0502
/
P(2)ꢁ
P(1)
P(2)
/C(61)
/
/
C(31)
c
/
/
125.35
124.07
C?ꢁ
/
/
121.71
a
/
/
Graphite monochromated.
b
c
Rꢁ
/
a½Foꢃ
/
Fc½/aFo½.
F2c)/aw(F2o)2]1/2; wꢁ
Rwꢁ
/
[aw(F2oꢃ
/
/
1/[s2(F2o)ꢂ
/
(aP)2]; Pꢁ
1/
/
3[F2oꢂ
/
2F2c].
yield along with the cyclopropane product 11, whereas
complex 10 gives exclusively product 11. The formation
of product 11 occurs thermally (80 8C, 3 h), in the
absence of catalyst in 55% yield [15]. Except for complex
6, all others afford 1,1-diphenyl ethene (13).
When a-methyl styrene was treated with Ph2CN2 in
the presence of complexes 3ꢀ10, the products obtained
ð1Þ
/
are shown in Scheme 4 and the yields of different
products are tabulated (Table 5). The cyclopropane
To determine the catalytic activities of the ruthenium
complexes 3ꢀ10, cyclopropanation of styrene deriva-
tives with Ph2CN2 was attempted. The reaction of
styrene with Ph2CN2 in the presence of complexes 3ꢀ
/
derivative 15 is obtained in 40ꢀ
complexes. Both the cis and trans cyclopropane deriva-
tives 17a and 17b were obtained in 15ꢀ45% yield.
/
50% with all the
/
/
10 gave the products as shown in Scheme 3 and the
yields are tabulated (Table 4). The reactions involving
Complex 6 gives only trans-1,2-diphenyl-1,2-dimethyl-
cyclopropane. 1,1,3,3-Tetraphenyl cyclobutane was ob-
tained in trace amount in all the reactions.
complexes 3ꢀ
/
9 afford propene derivative 12 in 8ꢀ16%
/

230
S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ235
/
Table 3
Table 4
Reaction of Ph2CN2 with styrene catalysed by 3ꢀ10
˚
Selected bond distances (A) and bond angles (8) for 4
/
Bond distances
Complex
T (8C)
Time (h)
Yield (%)
Ruꢁ
Ruꢁ
Ruꢁ
Ruꢁ
P(1)ꢁ
P(1)ꢁ
P(2)ꢁ
/
Cl
2.450(1)
2.302(1)
2.227(4)
2.182(4)
1.688(3)
1.847(3)
1.836(4)
1.402(5)
Ruꢁ
Ruꢁ
Ruꢁ
Ruꢁ
P(1)ꢁ
P(2)ꢁ
P(2)ꢁ
/
P(1)
C(1)
C(3)
C(5)
2.290(1)
2.235(4)
2.230(5)
2.189(3)
1.830(3)
1.700(3)
1.838(4)
1.410(4)
11
12 13 14
/
P(2)
C(2)
C(4)
/
/
/
3
4
55
55
60
60
75
75
75
75
6
6
7
7
7
7
7
7
74
74
71
83
72
60
59
99.9
8
13
12
ꢀ
ꢀ/
ꢀ/
ꢀ/
/
18
13
17
17
12
9
/
/
/N(1)
/
C(12)
N(2)
C(24)
5
/C(6)
/
6
ꢀ/
16
/C(36)
/
7
ꢀ/
N(1)ꢁ
Bond angles
ClꢁRuꢁP(1)
P(1)ꢁRuꢁ
RuꢁP(1)ꢁ
N(1)ꢁ
C(12)ꢁ
RuꢁP(2)ꢁ
N(2)ꢁP(2)ꢁ
C(36)ꢁP(2)ꢁ
P(2)ꢁN(2)ꢁC(30)
C?ꢁRuꢁP(2)
/
C(18)
N(2)ꢁC(30)
/
8
14 17
14 18
9
9
/
/
91.09(3)
97.64(3)
118.9(1)
104.2(2)
103.6(2)
111.2(1)
103.3(2)
106.8(2)
129.4(3)
122.67
Clꢁ
Ruꢁ
Ruꢁ
N(1)ꢁ
RuꢁP(2)ꢁ
RuꢁP(2)ꢁ
N(2)ꢁ
P(1)ꢁN(1)ꢁ
C?ꢁRuꢁ
C?ꢁRuꢁ
/
Ruꢁ
P(1)ꢁ
P(1)ꢁ
P(1)ꢁ
/
P(2)
N(1)
C(6)
C(6)
89.72(3)
112.1(1)
112.9(1)
103.6(2)
108.4(1)
123.1(1)
102.1(2)
133.8(3)
124.94
10
ꢀ/
ꢀ/
0.1
/
/
P(2)
/
/
/
/C(12)
/
/
/
P(1)ꢁ
P(1)ꢁ
C(36)
C(36)
C(24)
/C(12)
/
/
/
/C(6)
/
/
N(2)
/
/
/
/
C(24)
/
/
/
P(2)ꢁ
/C(24)
/
/
/
/C(18)
/
/
/
/P(1)
/
/
/
/C(1)
121.68
Scheme 4.
Table 5
Reaction of Ph2CN2 with a-methyl styrene catalysed by 3ꢀ
/10
Complex
T (8C)
Time (h)
Yield (%)
15 16 17a 17b 13 14
3
4
50
50
55
50
75
75
75
75
6
41 10
48
9
27
14
17
10
29
14
15
20
6
8
8
8
8
8
6
8
Scheme 2.
6
ꢀ/
ꢀ/
10
5
6.5
7
49 10 13
49 14
6
ꢀ/
ꢀ/
7
8
45 11 11
39 15 13
45 13 19
48 13 10
11
10
17
15
8
8
9
10
8
ꢀ/
6
8
Scheme 3.
When 4-methyl styrene was treated with Ph2CN2 in
the presence of complexes 3 and 6, the products
obtained are shown in Scheme 5 and the yields of
different products are tabulated (Table 6). The cyclo-
propane derivative 18 was obtained as the major
product. When complex 6 was used, the product 13
was not obtained as observed with other two styrenes.
Scheme 5.
All complexes 3ꢀ/10 show different catalytic activity
It is well known that many metal-mediated Cꢁ
/C
compared to [CpRuCl(PPh3)2] in the reactions between
styrenes and carbenes. The reaction of styrene with
diazocompound in the presence of complex 10 shows
very poor activity as it gives 99% cyclopropane deriva-
tive with trace amount of cyclobutane product.
bond-forming reactions using diazo compounds proceed
through a carbene intermediate [22,23]. The reactions
follow the mechanism proposed earlier by Werner [24]
and are shown in Scheme 6, which explains the
formation of all products (cyclopropane, propene and

S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ
/
235
231
Table 6
Reaction of Ph2CN2 with 4-methyl styrene catalysed by 3 and 6
Complex
T (8C)
Time (h)
Yield (%)
18 19 20a,b
13 14
3
6
80
80
8
8
22 10 26
57 11 24
15 27
8
ꢀ
/
Fig. 3. Variable temperature 31P-NMR (in C6D6) spectra of the
reaction of a-methyl styrene with diphenyldiazomethane (a) complex
10 at room temperature before the reaction, (b) after 1 h at 70 8C, (c)
after 3 h at 75 8C, (d) after the reaction is complete (recorded after 9 h
at room temperature).
When the reaction was carried out in an NMR tube in
the presence of complex 10 with a-methyl styrene, the
triplet due to PPh3 group became broad and then turned
to a doublet, whereas the doublet due to the chelate
complex deformed and appeared as a doublet of doublet
at 78.2 ppm and a doublet at 72.7 ppm which were
assigned to coordinated and uncoordinated phosphorus
centres of Ph2N(R)PPh2. This indicates that the catalytic
process involves the carbene intermediate ‘X’ and not
‘Y’. An additional peak appeared at 115.9 ppm at high
temperature and disappeared after 1 h which remains
unidentified. After 9 h complex 10 was regenerated, as
confirmed by its 31P-NMR spectrum shown in Fig. 3.
Scheme 6.
ethene) except for cyclobutane derivative. The product
1,1,3,3-tetraphenyl cyclobutane may be the result of
dimerisation of diphenyl ethene.
The reactions of styrenes with Ph2CN2 in the presence
of Ru(II) complexes are presumed to proceed through
carbene intermediates. When disubstituted complexes (4
and 6) were used the possible intermediate is [CpRu(ꢀ
CPh2)Cl(PPh2N(H)R)] (RꢁPh, C6H11). In the case of
monosubstituted complexes (3 and 5), the carbene
intermediate may be a mixture of complexes, [CpRu(ꢀ
CPh2)Cl(PPh3)] and [CpRu(ꢀCPh2)Cl(PPh2N(H)R)]
(RꢁPh, C6H11). The possible intermediates involving
the complexes 7ꢀ10 can be either [CpRu(ꢀ
CPh2)(Ph2PN(R)PPh2-kP)(PPh3)]Cl (X) or [CpRu(ꢀ
/
/
/
/
/
/
/
/
CPh2)(Ph2PN(R)PPh2-kP,kP)]Cl (Y). In order to iden-
tify the carbene intermediates in the reactions involving
the ionic complexes 7ꢀ10, a typical reaction was carried
/
out in an NMR tube in the presence of complex 10 and
was monitored by 31P-NMR spectroscopy. The 31P-
NMR spectroscopic features for the intermediates X and
Y are different; Y is anticipated to give a single
resonance, whereas for X two doublets (one for un-
coordinated PPh2 end and the other for PPh3) and a
doublet of doublet for coordinated PPh2 are expected.
3. Conclusion
The reactions of [CpRuCl(PPh3)2] with aminopho-
sphines, Ph2PN(H)R (Rꢁ
stituted and disubstituted ruthenium(II) complexes 3ꢀ
/
Ph, C6H11) afford monosub-
6
/

232
S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ235
/
depending upon the reaction conditions and the stoi-
chiometry. The ionic complexes of aminobis(pho-
and the residue obtained was crystallized from Et2O (5
ml) at r.t. to get orangeꢀred crystals of 3. Yield: 90%
(0.46 g, 0.0619 mmol). M.p.: 158ꢀ161 8C (dec.). Anal.
/
sphines) 7ꢀ
Complexes 3ꢀ
cyclopropanation and Cꢁ
nyldiazomethane and terminal alkene (styrene deriva-
tives). The catalytic activity of complexes 3ꢀ10 is
/
10 were obtained in moderate yield.
10 have been found to catalyse the
C coupling reaction of diphe-
/
/
Calc. for C41H36ClNP2Ru: C, 66.44; H, 4.89; N, 1.89.
/
Found: C, 66.74; H, 4.68; N, 1.75%. IR (KBr disk)
1
cmꢃ1: nNH: 3250 br m. H-NMR (CDCl3):d 8.00ꢀ
/
7.20
(m, phenyl, 30H) 5.20 (s, C5H5, 5H). 31P{1H}-NMR
/
different when compared to that of [CpRuCl(PPh3)2].
This could be due to the different substituents on
phosphorus atom and this difference in reactivity gives
scope for new catalytic conversions at metal centre.
Formation of 1,1,3,3-tetraphenyl cyclobutane was ob-
served for the first time in the cyclopropanation reac-
tions. Further investigation to isolate the carbene
intermediates in the catalytic cycle and to understand
the mechanism to get insight into the factors governing
chemo- and stereoselectivity are in progress in our
laboratory.
(CDCl3): d 42.9 (d, PPh3), 72.4 (d, PPh2) (2JPP
Hz).
ꢁ42.4
/
4.3. Preparation of [CpRuCl(PPh2N(H)Ph)2] (4)
To a solution of CpRuCl(PPh3)2 (0.05 g, 0.068 mmol)
in toluene (6 ml) was added Ph2PN(H)Ph (0.038 g, 0.13
mmol) in toluene (7 ml). The reaction mixture was
heated to 90 8C for 8 h. The reaction mixture was dried
under vacuo, and the orange red residue obtained was
washed with hot heptane (3ꢄ
from CH2Cl2ꢀn-hexane (2:1) mixture at ꢃ
was identified as 4. Yield: 75% (0.046 g, 0.0608 mmol).
M.p.: 200ꢀ202 8C (dec.). Anal. Calc. for
C41H37ClN2P2Ru: C, 65.12; H, 4.93; N, 3.70. Found:
C, 64.95; H, 4.84; N, 3.60%. IR (KBr disk) cmꢃ1: nNH
3256 br s. 1H-NMR (CDCl3): d 7.45ꢀ
7.16 (m, PPh,
7.5 Hz), 6.61 (t, N-
/5 ml) and crystallized
/
/
10 8C and
4. Experimental
/
4.1. General methods
:
/
3
All manipulations were performed under rigorously
anaerobic conditions using Schlenk techniques. Solvents
were dried and distilled under the nitrogen atmosphere
20H), 6.85 (t, N-Ph-m, 4H, JHH
Ph-p, 2H, 3JHH
ꢁ
/
ꢁ
/
7.5 Hz), 6.34 (d. N-Ph-o, 4H, 3JHH
ꢁ
/
7.8 Hz), 5.20 (s, C5H5, 5H). 31P{1H}-NMR (CDCl3): d
72.6 (s). MS (HRMS): 756.12 (m/z).
The heptane extract was evaporated to dryness and
prior to use. The aminophosphines, RN(H)PPh2 (Rꢁ
Ph, [25] C6H11 [17i]), bis(diphenylphosphino)amines,
RN(PPh2)2 (Rꢁ
Et, nPr, iPr [26], nBu [27]),
/
/
Et2O (3 ml) was added, which gave orangeꢀ/red crystals
CpRuCl(PPh3)2 [28] and Ph2CN2 [29] were prepared
according to the literature procedures, whereas styrene,
a-methyl styrene and 4-methyl styrene were purchased
from Aldrich and used without further purification.
NMR spectra were recorded using VXR 300 and Bruker
AMX 400 spectrometer and shifts were determined with
reference to deuterium signal of the solvent employed.
of 3. Yield: 20% (0.011 g, 0.014 mmol).
Complex, CpRuCl(PPh2N(H)Ph)2 (4) can also be
prepared from CpRuCl(PPh3)(PPh2N(H)Ph) (3). A
mixture of 3 (0.030 g, 0.04 mmol) and Ph2PN(H)Ph
(0.013 g, 0.048 mmol) in toluene (10 ml) was heated to
80 8C for 6 h. The reaction mixture was evaporated to
dryness and the residue obtained was washed with hot
1
The H-NMR chemical shifts are reported in ppm from
heptane (3ꢄ
hexane (2:1) mixture and cooled to ꢃ
orangeꢀred crystals of 4. Yield: 50% (0.015 g, 0.020
mmol).
/
5 ml) and re-dissolved in CH2Cl2ꢀ
/
n-
internal Me4Si and 31P-NMR spectra are reported in
ppm from external 85% H3PO4. Positive values indicate
downfield shifts. IR spectra were recorded on a Nicolet
Impact 400 FT IR instrument in KBr disk. Microana-
lyses were performed on a Carlo Erba model 1112
elemental analyser. Melting points were determined in
capillary tubes and were not corrected. High-resolution
mass spectra (HRMS) were recorded on MASPEC
/
10 8C to give
/
4.4. Preparation of
[CpRuCl(PPh2N(H)C6H11)(PPh3)] (5)
A mixture of CpRuCl(PPh3)2 (0.05 g, 0.068 mmol)
and PPh2N(H)C6H11 (0.019 g, 0.068 mmol) in CH2Cl2
(7 ml) was stirred at r.t. for 8 h. The solvent was
evaporated under reduced pressure and the residue
obtained was crystallized from Et2O (5 ml) at r.t. to
(msco/9849) system. GCꢀMS measurements were per-
/
formed with HP G1800A GCD instrument.
4.2. Preparation of [CpRuCl(PPh3)(Ph2PN(H)Ph)]
(3)
give orangeꢀ
product, 5. Yield, 83% (0.043 g, 0.057 mmol). M.p.:
158ꢀ161 8C (dec.). Anal. Calc. for C41H42ClNP2Ru: C,
/red crystalline solid identified as the
A mixture of CpRuCl(PPh3)2 (0.05 g, 0.068 mmol)
and Ph2PN(H)Ph (0.019 g, 0.068 mmol) in CH2Cl2 (7
ml) was stirred at room temperature (r.t.) for 8 h. The
reaction mixture was evaporated under reduced pressure
/
65.90; H, 5.66; N, 1.87%. Found: C, 66.14; H, 5.49; N,
1
1.78%. IR (KBr disk) cmꢃ1: nNH: 3250 br m. H-NMR
(CDCl3):d 7.98ꢀ7.02 (m, phenyl, 25H), 4.14 (s, C5H5,
/

S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ
/
235
233
3
(t, CH3, 3H, JHH
5H), 3.87 (m, NH, 1H), 2.56ꢀ
31P{1H}-NMR (CDCl3): d 42.9 (d, PPh3, 1P), 77.9 (d,
PPh2, 1P) (2JPP
48.5 Hz). MS (HRMS): 747.11 (m/z).
/
0.77 (m, C6H11, 11H).
ꢁ
/
6.96 Hz). 31P{1H}-NMR (CDCl3):
34.7 Hz).
d 44.6 (t, PPh3, 1P), 82.7 (d, PPh2, 2P) (2JPP
ꢁ
/
ꢁ
/
4.9. [CpRu(PPh2N(iPr)PPh2)(PPh3)]Cl (9)
4.5. Preparation of [CpRuCl(PPh2N(H)C6H11)2] (6)
Yield: 65% (0.040 g, 0.045 mmol). M.p.: 212ꢀ
(dec.). Anal. Calc. for C50H47ClNP3Ru×0.5CH2Cl2: C,
64.96; H, 5.18; N, 1.49%. Found: C, 65.04; H, 5.15; N,
1.33%. 1H-NMR (CDCl3): d 7.59ꢀ
6.97 (m, phenyl,
35H), 4.36 (s, C5H5, 5H), 4.07 (septet, CH, 1H,
/
213 8C
/
A mixture of CpRuCl(PPh3)2 (0.05 g, 0.068 mmol)
and Ph2PN(H)C6H11 (0.049 g, 0.172 mmol) in toluene
(12 ml) was heated to 95 8C for 12 h. The solution was
evaporated to dryness under reduced pressure and the
/
3JHH
31P{1H}-NMR (CDCl3): d 45.8 (t, PPh3, 1P), 80.8 (d,
PPh2, 2P) (2JPP
36.3 Hz).
ꢁ
/
6.96 Hz), 0.92 (d, CH3, 6H, JHH
ꢁ6.96 Hz).
/
3
residue obtained was washed with n-hexane (5ꢄ
The orangeꢀred residue was crystallized from CH2Cl2ꢀ
n-hexane (2:1) mixture at ꢃ10 8C and was identified as
6. Yield: 69% (0.047 g, 0.047 mmol). M.p.: 180ꢀ182 8C
/3 ml).
/
/
ꢁ
/
/
/
4.10. [CpRu(PPh2N(nBu)PPh2)(PPh3)]Cl (10)
(dec.). Anal. Calc. for C41H49ClN2P2Ru: C, 64.10; H,
6.43; N, 3.65. Found: C, 63.74; H, 6.41; N, 3.76%. IR
1
(KBr disk) cmꢃ1: nNH: 3318 s. H-NMR (CD2Cl2):d
Yield: 46% (0.029 g, 0.032 mmol). M.p.: 218ꢀ221 8C
/
(dec.). Anal. Calc. for C51H49ClNP3Ru: C, 67.65; H,
5.45; N, 1.56%. Found: C, 67.61; H, 5.46; N, 1.55%. 1H-
7.98ꢀ
/
7.04 (m, phenyl, 20H), 4.12 (s, C5H5, 5H), 2.90ꢀ
/
0.44 (m, C6H11, 22H). 31P{1H}-NMR (CD2Cl2): d 81.8
(s). MS (HRMS): 768.21 (m/z).
The n-hexane filtrate was evaporated under reduced
NMR (CDCl3): d 7.54ꢀ/6.85 (m, phenyl, 35H), 4.58 (s,
C5H5, 5H), 3.24 (m, CH2, 2H), 1.34 (m, CH2, 2H), 1.04
3
(sextet, CH2, 2H, JHH
3JHH 7.28 Hz). 31P{1H}-NMR (CDCl3): d 44.1 (t,
PPh3, 1P), 82.0 (d, PPh2, 2P) (2JPP
34.8 Hz).
ꢁ
/
7.28 Hz), 0.68 (t, CH3, 3H,
pressure and Et2O (5 ml) was added and cooled to 0 8C
to result in orangeꢀ
0.027 mmol).
ꢁ
/
/red crystals of 5. Yield: 39% (0.02 g,
ꢁ
/
4.11. Catalytic cyclopropanation of alkenes with
diphenyldiazomethane
4.6. Preparation of [CpRu(PPh2N(R)PPh2)(PPh3)]Cl
n
i
n
(RꢁEt, 7; Pr, 8; Pr, 9; Bu, 10)
/
All experimental details are given in Tables 4ꢀ
typical procedure, 0.005 mmol of the complex (3ꢀ
/
6. In a
To a stirring solution of CpRuCl(PPh3)2 (0.050 g,
0.069 mmol) in toluene (5 ml) was added a solution of
/10)
was dissolved in corresponding alkene (1 ml). A mixture
of Ph2CN2 (1 mmol) and alkene (2 ml) was added to the
catalyst and heated to an appropriate temperature. Then
the reaction mixture was stirred for an appropriate time
and the crude oil was chromatographed on a column of
silica gel and eluted with n-hexane and CH2Cl2 to
separate cyclopropane, propene and cyclobutane deri-
i
PPh2N(R)PPh2 (Rꢁ
/
Et, nPr, Pr, nBu) (0.069 mmol)
also in toluene (5 ml) and the reaction mixture was
heated to 100ꢀ Pr). The
105 8C for 10 h (12 h when Rꢁi
yellow solid precipitated out was filtered and washed
with Et2O (3ꢄ5 ml) and crystallized from CH2Cl2ꢀn-
hexane (2:1) mixture to give analytically pure products,
7ꢀ10.
/
/
/
/
/
vatives, which are detected in the reaction mixtures by
1
GCꢀ
data. Yields given in Tables 4ꢀ
GCꢀMS.
/
MS and also identified by H-NMR spectroscopic
4.7. [CpRu(PPh2N(Et)PPh2)(PPh3)]Cl (7)
Yield: 52% (0.035 g, 0.039 mmol). M.p.: 214ꢀ
(dec.). Anal. Calc. for C49H45ClNP3Ru: C, 67.08; H,
/
6 are calculated based on
/
/
218 8C
4.12. X-ray crystallography
1
5.17; N, 1.60. Found: C, 67.12; H, 5.21; N, 1.56%. H-
NMR (CDCl3): d 7.51ꢀ
C5H5, 5H), 3.43 (m, CH2, 2H), 1.05 (t, CH3, 3H, 3JHH
7.16 Hz). 31P{1H}-NMR (CDCl3): d 44.1 (t, PPh3, 1P),
82.7 (d, PPh2, 2P), (2JPP
34.6 Hz).
/
6.84 (m, phenyl, 35H), 4.58 (s,
Crystals of compounds 3 and 4 obtained as described
above were mounted on Pyrex filaments with epoxy
resin. Bruker P4/Ra/SMART 1000 CCD diffractometer
(for compound 3) and Nonius MACH3 diffractometer
(for compound 4) were used for the unit cell determina-
tion and intensity data collection. The initially obtained
unit cell parameters were refined by accurately centring
ꢁ
/
ꢁ
/
4.8. [CpRu(PPh2N(nPr)PPh2)(PPh3)]Cl (8)
Yield: 61% (0.038 g, 0.042 mmol). M.p.: 232ꢀ
/
235 8C
randomly selected 25 reflections in the u ranges (7.48ꢀ
/
(dec.). Anal. Calc. for C50H47ClNP3Ru: C, 67.37; H,
1
5.31; N, 1.57. Found: C, 67.04; H, 5.22; N, 1.56%. H-
12.428) for compound 4. Periodic monitoring of check
reflections showed stability of the intensity data. Details
of the crystal and data collection are given in Table 1.
The data were corrected by SADABS correction method
NMR (CDCl3): d 7.55ꢀ
/
6.84 (m, phenyl, 35H), 4.60 (s,
C5H5, 5H), 3.19 (m, CH2, 2H), 1.45 (m, CH2, 2H), 0.67

234
S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ235
/
Shaver, P.G. Hayes, S.A. Westcott, Can. J. Chem. 79 (2001) 1898;
(d) A. Zanotti-Gerosa, C. Malan, D. Herzberg, Org. Lett. 3 (2001)
3687;
and the structure was solved by direct methods (SHELXS
93) and the calculations were performed with the
SHELXL 93 [30,31] program for compound 3, whereas
for compound 4, the data correction was done by psi
scan method and the structure was solved by direct
methods (SHELXS 97) and refined using SHELXL 97
software [32]. The non-hydrogen atoms were refined
with anisotropic thermal parameters. All the hydrogen
atoms were geometrically fixed and allowed to refine
using riding model.
(e) C. Bianchini, M. Frediani, F. Vizza, Chem. Commun. (2001)
479;
(f) F.J. Parlevliet, C. Kiener, J. Fraanje, K. Goubitz, M. Lutz,
A.L. Spek, P.C.J. Kamer, P.W.N.M. van Leeuwen, J. Chem. Soc.
Dalton Trans. (2000) 1113.
[4] (a) L. Qiu, J. Qi, C.-C. Pai, S. Chan, Z. Zhou, M.C.K. Choi,
A.S.C. Chan, Org. Lett. 4 (2002) 4599;
(b) Y.-G. Zhou, W. Tang, W.-B. Wang, W. Li, X. Zhang, J. Am.
Chem. Soc. 124 (2002) 4952;
(c) P. Barbaro, C. Bianchini, A. Meli, M. Moreno, F. Vizza,
Organometallics 21 (2002) 1430;
(d) C. Allasia, M. Castiglioni, R. Giordano, E. Sappa, F. Verre, J.
Cluster Chem. 11 (2000) 493.
5. Supplementary material
[5] M. Urbala, M. Antoszczyszyn, S. Krompiec, Technologia Che-
miczna na Przelomie Wiekow (2000) 383.
Full details of data collection and structure refine-
ment have been deposited with the Cambridge Crystal-
lographic Data Centre, CCDC nos. 217068 and 217069
for compounds 3 and 4, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
[6] U. Matteoli, M. Bianchi, P. Frediani, G. Menchi, C. Botteghi, M.
Marchetti, J. Organomet. Chem. 263 (1984) 243.
[7] J.G. De Vries, G. Roelfes, R. Green, Tetrahedron Lett. 39 (1998)
8329.
[8] G. Jenner, E.M. Nahmed, H. Leismann, J. Organomet. Chem.
387 (1990) 315.
[9] C.W. Jung, P.E. Garrou, Organometallics 1 (1982) 658.
[10] C. Bergounhou, P. Fompeyrine, G. Commenges, J.J. Bonnet, J.
Mol. Catal. 48 (1988) 285.
UK (Fax: ꢂ44-1223-336033; e-mail: deposit@ccdc.ca-
m.ac.uk or www: http://www.ccdc.cam.ac.uk).
/
[11] H. Imai, T. Nishiguchi, M. Kobayashi, K. Fukuzumi, Bull. Chem.
Soc. Jpn. 48 (1975) 1585.
[12] (a) S.D. Ittel, C.A. Tolman, A.D. English, J.P. Jesson, J. Am.
Chem. Soc. 100 (1978) 7577;
Acknowledgements
(b) J.W. Rathke, E.L. Muetterties, J. Am. Chem. Soc. 97 (1975)
3272;
Department of Science and Technology (DST) and
Council of Scientific and Industrial Research (CSIR),
New Delhi, are acknowledged for the financial support
of this work. S.P. is thankful to CSIR, New Delhi, for
JRF and SRF fellowships. We also thank the Regional
Sophisticated Instrumentation Center (RSIC), Bombay;
Sophisticated Instrumentation Facility (SIF), Bangalore
and the Department of Chemistry, University of Alber-
ta, Edmonton, Canada for spectral facility.
(c) H.H. Karsch, H.F. Klein, H. Schmidbaur, Angew. Chem. Int.
Ed. Engl. 14 (1975) 637;
(d) J.F. Hartwig, R.A. Anderson, R.G. Bergman, Organometal-
lics 10 (1991) 1875;
(e) M. Antberg, L. Dahlenberg, Angew. Chem. Int. Ed. Engl. 25
(1986) 260;
(f) P.J. Desrosiers, R.S. Shinomoto, T.C. Flood, J. Am. Chem.
Soc. 108 (1986) 1346;
(g) R.S. Shinomoto, P.J. Desrosiers, G.P. Harper, T.C. Flood, J.
Am. Chem. Soc. 110 (1988) 7915.
[13] J.F. Hartwig, R.A. Anderson, R.G. Bergman, Organometallics 10
(1991) 1710.
References
[14] (a) F. Zaragoza Dorwald, Metal Carbenes in Organic Synthesis,
Wiley-VCH, Weinheim, 1999;
(b) K.J. Davis, D. Sinou, J. Mol. Catal. A 117 (2002) 173;
(c) K. Grela, M. Bieniek, Tetrahedron Lett. 42 (2001) 6425;
(d) D. Bentz, S. Laschat, Synthesis (2000) 1766.
[15] W. Baratta, W.A. Herrmann, R.M. Kratzer, P. Rigo, Organo-
metallics 19 (2000) 3664.
[1] (a) A.F. Noels, A. Demonceau, in: B. Cornil, W.A. Herrmann
(Eds.), Applied Homogeneous Catalysis by Organometallic Com-
plexes, vol. 2, VCH, Weinheim, 1996, p. 733;
(b) A. Pfaltz, Acc. Chem. Res. 26 (1993) 339;
(c) R. Schumacher, F. Dammest, H.-U. Reissig, Chem. Eur. J. 3
(1997) 614;
[16] O. Tutusaus, S. Delfosse, A. Demonceau, A.F. Noels, R. Nunez,
C. Vinas, F. Teixidor, Tetrahedron Lett. 43 (2002) 983.
[17] (a) M.S. Balakrishna, R.M. Abhyankar, J.T. Mague, J. Chem.
Soc. Dalton Trans. (1999) 1407;
(d) K. Wada, D. Izuhara, K. Yamada, M. Shiotsuki, T. Kondo,
T.-A. Mitsudo, Chem. Commun. (2001) 1802;
(e) S.-I. Murahashi, H. Takaya, T. Naota, Pure Appl. Chem. 74
(2002) 19.
(b) M.S. Balakrishna, R.M. Abhyankar, M.G. Walawalker,
Tetrahedron Lett. 42 (2001) 2733;
[2] (a) A. Jourdant, E. Gonzalez-Zamora, J. Zhu, J. Org. Chem. 67
(2002) 3163;
(c) M.S. Balakrishna, R. Panda, J.T. Mague, Inorg. Chem. 40
(2001) 5620;
(b) L. Rosenberg, C.W. Davis, J. Yao, J. Am. Chem. Soc. 123
(2001) 5120;
(d) M.S. Balakrishna, R. Panda, J.T. Mague, J. Chem. Soc.
Dalton Trans. (2002) 4617;
(c) F. Barriere, W.E. Geiger, Organometallics 20 (2001) 2133.
[3] (a) L. Gonsalvi, H. Adams, G.J. Sunley, E. Ditzel, A. Haynes, J.
Am. Chem. Soc. 124 (2002) 13597;
(e) M.S. Balakrishna, M.G. Walawalker, J. Organomet. Chem.
628 (2001) 76;
(b) P. Kandanarachchi, A. Guo, Z. Petrovic, J. Mol. Catal. A 184
(2002) 65;
(c) C.M. Vogels, P.E. O’Connor, T.E. Phillips, K.J. Watson, M.P.
(f) M.S. Balakrishna, R. Panda, D.C. Smith, Jr., A. Klaman, S.P.
Nolan, J. Organomet. Chem. 599 (2000) 159;
(g) M.S. Balakrishna, K. Ramaswamy, R.M. Abhyankar, J.

S. Priya et al. / Journal of Organometallic Chemistry 688 (2003) 227ꢀ
/
235
235
Organomet. Chem. 560 (1990) 131;
[23] I. Goettker-Schnetmann, R. Aumann, Organometallics 20 (2001)
346.
(h) S. Priya, M.S. Balakrishna, J.T. Mague, Inorg. Chem.
Commun. 4 (2001) 437;
[24] H. Werner, J. Organomet. Chem. 500 (1995) 331.
[25] W. Wiegrabe, H. Bock, Chem. Ber. 101 (1968) 1414.
[26] M.S. Balakrishna, T.K. Prakasha, S.S. Krishnamurthy, U.
Siriwardane, N.S. Hosmane, J. Organomet. Chem. 390 (1990)
203.
(i) S. Priya, M.S. Balakrishna, J.T. Mague, S.M. Mobin, Inorg.
Chem. 42 (2003) 1272.
[18] M.I. Bruce, F.S. Wong, B.W. Skelton, A.H. White, J. Chem. Soc.
Dalton Trans. (1981) 1398.
[27] G. Ewart, A.P. Lane, J. McKechnie, D.S. Payne, J. Chem. Soc.
(1964) 1543.
[19] M.I. Bruce, M.P. Cifuentes, M.R. Snow, R.T. Tiekink, J.
Organomet. Chem. 359 (1989) 379.
[28] M.I. Bruce, N. Windsor, Aust. J. Chem. 30 (1977) 1601.
[29] J.B. Miller, J. Org. Chem. 24 (1959) 560.
[30] G.M. Sheldrick, Acta Crystallogr. A46 (1990) 467.
[31] G.M. Sheldrick, SHELXL-93. Program for Crystal Structure
[20] J. Ellermann, C. Schelle, F.A. Knoch, M. Moll, D. Pohl,
Monatsh. Chem. 127 (1996) 783.
[21] H. Tomioka, K. Ohno, Y. Izawa, R.A. Moss, R.C. Munjal,
Tetrahedron Lett. 25 (1984) 5415.
Refinement 1993, University of Gottingen, Gottingen, Germany.
¨ ¨
[32] G.M. Sheldrick, SHELXL-97. Program for Crystal Structure
Refinement 1997, University of Gottingen, Gottingen, Germany.
[22] J. Wolf, L. Brandt, A. Fries, H. Werner, Angew. Chem. Int. Ed.
Engl. 29 (1990) 510.
¨
¨