Reactions of aminophosphines and aminobis(phosphines) with aldehydes and ketones: Coordination complexes of the resultant aminobis(alkylphosphineoxides) with cobalt, uranium, thorium and gadolinium salts: Crystal and molecular structures of Ph2P(O)CH(C6H4OH-o)N(H)Ph, Ph2P(O)CH(OH)C6H4OH-o and Ph 2P(O)N(H)Ph

Article abstract of DOI:10.1016/j.poly.2005.04.036

The reaction of aminophosphines and aminobis(phosphines) with aldehydes leads to either insertion of carbon fragments into the P(III)-N bonds or formation of α-hydroxyphosphine oxides through P(III)-N bond cleavage. Reaction of 1,2-C₆H₄{N(H)PPh₂}₂ with paraformaldehyde gives the P(III)-N bond inserted product 1,2-C ₆H₄{N(H)CH₂P(O)Ph₂}₂, whereas 1,3-C₆H₄{N(H)PPh₂}₂ forms an analogous product but with an additional methylene group inserted between the two nitrogen centers through nucleophilic addition to form a bicyclic derivative, 1,3-C₆H₄{Ph₂P(O)CH ₂N(μ-CH₂)NCH₂P(O)Ph₂}. Reactions of Ph₂PN(H)Ph with aromatic aldehydes, RCHO (R = C₆H ₄OH-o, 5-BrC₆H₃OH-o, (η⁵-C ₅H₅)Fe(η⁵-C₅H₄-)) lead to the insertion of 'RCH' into the P(III)-N bond to give Ph ₂P(O)CH(R)N(H)Ph. The reactions of aminobis(phosphine), Ph ₂PN(ⁿBu)PPh₂ with both aromatic and aliphatic aldehydes lead to the formation of α-hydroxy phosphine oxide derivatives of the type Ph₂P(O)CH(R)OH, through P(III)-N bond cleavage. The N-bridged bis(phosphine oxide) ⁿPrN(CH₂P(O)Ph ₂)₂ readily forms chelate complexes with U(VI), Th(IV) and Gd(III) derivatives.

Full text of DOI:10.1016/j.poly.2005.04.036

Polyhedron 24 (2005) 1641–1650
www.elsevier.com/locate/poly
Reactions of aminophosphines and aminobis(phosphines)
with aldehydes and ketones: Coordination complexes of the resultant
aminobis(alkylphosphineoxides) with cobalt, uranium, thorium
and gadolinium salts
Crystal and molecular structures of Ph P(O)CH(C H OH-o)N(H)Ph,
2
6 4
Ph P(O)CH(OH)C H OH-o and Ph P(O)N(H)Ph
2
2
6 4
*
Srinivasan Priya, Maravanji S. Balakrishna , Shaikh M. Mobin
Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076, India
Received 17 February 2005; accepted 15 April 2005
Available online 14 July 2005
Abstract
The reaction of aminophosphines and aminobis(phosphines) with aldehydes leads to either insertion of carbon fragments into the
P(III)–N bonds or formation of a-hydroxyphosphine oxides through P(III)–N bond cleavage. Reaction of 1,2-C
with paraformaldehyde gives the P(III)–N bond inserted product 1,2-C {N(H)CH P(O)Ph , whereas 1,3-C
6
H
H
4
{N(H)PPh
{N(H)PPh
2
}
}
2
2
6
H
4
2
2 2
}
6
4
2
forms an analogous product but with an additional methylene group inserted between the two nitrogen centers through nucleophilic
addition to form a bicyclic derivative, 1,3-C {Ph P(O)CH N(l-CH )NCH P(O)Ph }. Reactions of Ph PN(H)Ph with aromatic
aldehydes, RCHO (R = C OH-o, 5-BrC OH-o, (g -C –)) lead to the insertion of ꢀRCHꢁ into the P(III)–N bond
6
H
4
2
2
2
2
2
2
5
5
H
6 4
6
H
3
5 5 5 4
H )Fe(g -C H
n
to give Ph P(O)CH(R)N(H)Ph. The reactions of aminobis(phosphine), Ph PN( Bu)PPh with both aromatic and aliphatic alde-
2
2
2
hydes lead to the formation of a-hydroxy phosphine oxide derivatives of the type Ph
2
P(O)CH(R)OH, through P(III)–N bond cleav-
n
age. The N-bridged bis(phosphine oxide) PrN(CH
derivatives.
2 2 2
P(O)Ph ) readily forms chelate complexes with U(VI), Th(IV) and Gd(III)
ꢀ
2005 Elsevier Ltd. All rights reserved.
Keywords: Aminophosphines; Insertion; a-Hydroxy phosphine oxides; Coordination; P–N bond cleavage; Crystal structure
1
. Introduction
tems [1]. However, P(III)–N bonds can undergo hydro-
lytic cleavage in the presence of trace amounts of acid/
base impurities [3]. Even during complexation reactions
with transition metals, P(III)–N bonds can undergo
cleavage as demonstrated by King [4], Burrows [5] and
also our research group [6]. Previously we have reported
the insertion of carbon fragments into the P(III)–N
bonds and the coordination chemistry of the resulting
phosphine oxides [7]. As a part of our interest on multi-
functional phosphines and aminophosphines and their
catalytic applications [8,6b], herein we report the reac-
tions of aminophosphines and aminobis(phosphines)
The stability of P(III)–N bonds in cyclic and acyclic
phosphazanes depends to a large extent on the phospho-
rus and nitrogen substituents [1]. P(III)–N bonds are
stable to lithium and Grignard reagents [2] and can sur-
vive a variety of nucleophilic substitution reactions at
the phosphorus centers both in cyclic and acyclic sys-
*
Corresponding author. Tel.: +91 22 2576 7181; fax: +91 22 2576
152/22 2572 3480.
E-mail address: krishna@iitb.ac.in (M.S. Balakrishna).
7
0
277-5387/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.04.036

1642
S. Priya et al. / Polyhedron 24 (2005) 1641–1650
with aldehydes and ketones. The molecular structures
and the complexing ability of some of the bisphosphine
oxides thus obtained are also described.
H
N
O
H
N
PPh2
PPh2
2
(HCHO)n
O
N
1
N
PPh2
H
PPh2
2
H
2
. Results and discussion
The aminophosphines, Ph PN(H)Ph, Ph PN( Bu)-
PPh2 and 1,2-C H (N(H)PPh ) were prepared as
H
N
n
2
2
PPh2
PPh2
2
(HCHO)n
6
4
2 2
N
N
H
H
described in the literature (see Section 4). The 1,3-pheny-
lenediamine derivative 1,3-C H (N(H)PPh ) (1) was
Ph P
2
PPh2
N
H
O
6
4
2 2
O
prepared in 46% yield by reacting chlorodiphenylphos-
phine with 1,3-phenylenediamine in THF in the presence
of a catalytic amount of 4-dimethylaminopyridine. The
3
(HCHO)n
2 (HCHO)n
ꢀ1
31
IR spectrum of 1 shows mNH at 3218 cm and the
NMR spectrum of 1 exhibits a single resonance at
5.2 ppm. The structural composition was further con-
P
N
N
N
N
3
H
Ph P
PPh2
PPh2
O
2
HO
Ph P
firmed by mass spectral and micro analytical data.
The reaction of 1 with two equivalents of parafor-
maldehyde affords the P–N bond inserted product,
2
O
O
O
3
Scheme 1.
1
gous reaction of Ph PNC H NPPh with paraformal-
,3-C H (N(H)CH P(O)Ph ) (2) similar to the analo-
6 4 2 2 2
2
2
4
2
3
The P NMR spectra of compounds 5 and 6 show
1
dehyde, reported earlier [7b]. The reaction of 1 with
one equivalent of paraformaldehyde did not give a
single resonances at 37.8 and 29.2 ppm, respectively.
1
The H NMR spectrum of 5 shows a doublet at
monofunctionalized product of the type Ph PN(H)-
2
2
5.5 ppm for the CH protons with a J
C H N(H)CH P(O)Ph , instead compound 2 was ob-
6
4
2
2
coupling of
PH
tained in 35% yield with half of the reactant 1 left
5.9 Hz whereas for 6 the analogous signal appears as
a broad singlet at 5.1 ppm. The spectroscopic data
of 4 is given in our previous report [7b].
3
unreacted in the solution. The P NMR spectrum
1
of 2 shows a single resonance at 28.7 ppm and the
1
methylene protons appear at 2.39 ppm in its
H
H
NMR spectrum. Interestingly, the reaction of 1,2-
C H (N(H)PPh ) with two equivalents of paraformal-
dehyde afforded a similar product but containing three
Ph
N
PPh + RCHO
2
6
4
2 2
O
1
methylene groups as indicated by its H NMR spec-
H
PPh2
Ph
N
trum (Scheme 1). When the reaction was carried out
using three equivalents of paraformaldehyde the yield
was almost quantitative indicating the insertion of
two methylene groups into two P(III)–N bonds and
another one between two nitrogen centers through nucle-
ophilic addition to give a product of the type, 1,2-
C H {N(CH P(O)Ph )(l-CH )N(CH P(O)Ph )} (3) in
ð1Þ
H
R
R = C H OH-o, 4
6
4
5
-Br-C H OH-o, 5
6 3
(
C H )Fe(C H ), 6
5 5 5 4
6
4
2
2
2
2
2
3
1
quantitative yield. The P NMR spectrum of 3 shows
1
a single resonance at 26.6 ppm. In the H NMR spec-
The structure of Ph P(O)CH(C H OH-o)N(H)Ph (4)
2 6 4
was confirmed by single crystal X-ray diffraction studies
and is shown in Fig. 1. Crystal data and the details of
the structure determination are given in Table 1 while
selected bond lengths and inter bond angles are listed
in Table 2. The asymmetric unit of compound 4 contains
two identical independent molecules but the correspond-
ing bond lengths and bond angles are not significantly
different. The P–O bond distances are P(1)–O(1) =
trum of 3, the protons due to the methylene groups
inserted into the P–N bonds appear at 3.82 ppm as
broad singlets, whereas the bridging methylene pro-
tons resonate at 4.96 ppm. When the aminophosphines
are treated with aromatic aldehydes, the ꢀCH(R)ꢁ
groups insert into the P–N bonds followed by oxida-
tion of the phosphorus from P(III) to P(V), whereas
aliphatic aldehydes, such as butylaldehyde, afford an
a-hydroxy phosphine oxide through P–N bond cleav-
˚
1.522(9), P(2)–O(3) = 1.458(9) A and the P–C bond dis-
˚
tances are in the range 1.720(14)–1.872(11) A. The geo-
age [7b]. The reactions of Ph PN(H)Ph with RCHO
afford P–N inserted products Ph P(O)CH(R)N(H)Ph
metry around the nitrogen is strictly planar and the sum
of the angles is 360ꢁ. Although in the lattice the mole-
cules exhibit intra and inter molecular O–H---O type
interactions, they are not significantly prominent.
2
2
5
(
(
R = C H OH-o, 4; 5-BrC H OH-p, 5; (g -C H )Fe-
g -C H ), 6) in 65–85% yield as shown in Eq. (1).
6
4
6
3
5
5
5
5
4

S. Priya et al. / Polyhedron 24 (2005) 1641–1650
1643
Table 2
˚
Selected bond distances (A) and bond angles (ꢁ) of 4
Bond distances
P(1)–O(1)
P(1)–C(1)
P(1)–C(7)
P(1)–C(13)
C(13)–N(1)
N(1)–C(20)
1.522(9)
P(2)–O(3)
1.458(9)
1.845(12)
1.762(13)
1.819(9)
1.383(17)
1.470(15)
1.721(14)
1.770(13)
1.871(11)
1.449(15)
1.382(16)
P(2)–C(26)
P(2)–C(20)
P(2)–C(32)
C(45)–N(2)
N(2)–C(38)
Bond angles
O(1)–P(1)–C(1)
O(1)–P(1)–C(7)
O(1)–P(1)–C(13)
C(1)–P(1)–C(13)
C(1)–P(1)–C(7)
C(7)–P(1)–C(13)
C(20)–N(1)–C(13)
111.0(6)
O(3)–P(2)–C(38)
O(3)–P(2)–C(32)
O(3)–P(2)–C(26)
C(32)–P(2)–C(38)
C(38)–P(2)–C(26)
C(26)–P(2)–C(32)
C(45)–N(2)–C(38)
111.7(5)
115.4(5)
108.8(5)
109.1(6)
106.7(6)
105.4(6)
120.0(10)
113.7(6)
109.4(6)
105.5(6)
108.9(6)
107.4(6)
121.3(10)
2 6 4
Fig. 1. Molecular structure of Ph P(O)CH(C H OH-o)N(H)Ph (4)
with the atom numbering scheme. The ellipsoids are drawn at the 50%
probability level.
n
n
The reactions of BuN(PPh ) with RCHO (R = Pr,
2
2
distances and bond angles are very similar. The struc-
ture of 9 shows a distorted tetrahedral geometry around
the phosphorus centers. The P@O bond distance varies
Ph, C H OH-o, OC H ) gave a-hydroxy phosphine oxi-
6
4
4
3
n
des, Ph P(O)CH(OH)R (R = Pr, 7; Ph, 8; C H OH-o,
2
6
4
9
; OC H , 10) in 40–45% yields (Scheme 2). The forma-
4 3
tion of these products may be due to the prior cleavage
of the P–N bond through the elimination of primary
amine to form Ph P(O)H, which then reacts with the
PPh2
O
O
O
CHO
R'
N
PPh2
2
n
R' = Pr
PPh2
N
aldehyde to give Ph P(O)CH(OH)R. Compounds 7–10
2
ꢀ
1
around 3200–3250 cm in their IR spectra.
n
R' = Pr
show m
The P NMR spectra of 7–10 show a single resonance
PPh2
O
OH
n
3
1
Bu
O
1
in the range of 30–37 ppm and the H NMR spectra
show doublets around 4.4–5.5 ppm for the CH proton,
2
with J couplings in the range of 5–10 Hz.
CHO
RCHO
O
n
O
R' = Bu
PH
O
PPh2
R
The structure of Ph P(O)CH(OH)C H OH-o (9) is
6
2
4
PPh2
established by single crystal X-ray diffraction studies
and the perspective view of the molecule is shown in
Fig. 2. The crystallographic data, selected bond dis-
tances and inter bond angles are listed in Tables 1 and
3, respectively. The asymmetric unit contains two iden-
tical independent molecules but the corresponding bond
H
O
HO
H
n
HO
R = Pr,
C H
7
8
10
6
5,
C H OH-o, 9
6
4
Scheme 2.
Table 1
Crystallographic data for 4, 9 and 11
Compound 4
Compound 9
Compound 11
Empirical formula
Formula weight
Crystal system
Space group
C
25
H
22NO
399.41
orthorhombic
Pbc2 (No. 29)
2
P
C
19
H
17
O
3
P
18
C H16NOP
324.30
monoclinic
P2 /c (No. 14)
293.29
orthorhombic
1
1
1
Pca2 (No. 29)
˚
a (A)
12.567(2)
16.452(1)
20.968(1)
90
5.678(1)
24.500(2)
25.552(4)
90
9.590(3)
9.698(1)
16.985(3)
90
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
90
92.06(1)
90
90
90
˚
3
V (A )
4335.2(8)
8
1.224
3552.3(7)
8
1579.7(6)
4
Z
ꢀ1
D
calc (g cm
)
1.213
0.2
1.233
0.2
ꢀ1
l (Mo Ka) (mm
Theta range (ꢁ)
Temperature (K)
)
0.2
1.62–24.92
293(2)
0.0757
0.1194
1.1–24.9
293
2.12–24.92
293(2)
0.0395
0.0886
R
0.084
0.281
R
w

1644
S. Priya et al. / Polyhedron 24 (2005) 1641–1650
3
Ph P(O)N(H)Ph (11). The P NMR spectrum of 11
1
2
shows a single resonance at 18.5 ppm. The structure of
1
1 was confirmed by a single crystal X-ray structure
determination. A perspective view of the molecule 11
is shown in Fig. 3(a) and the selected bond distances
and bond angles are given in Table 4. The P–O and
P–C distances are comparable with the literature for
compounds of a similar type [9–12]. The phosphorus is
in a tetrahedral environment as in other phosphine oxi-
des. Compound 11 shows intermolecular P@O. . .H–N
type hydrogen bonding interaction [dH(IN)–O(1)
=
˚
.06(5) A; d
˚
= 2.807(6) A; N(1)–H(1N)–O(1) =
N(1N)–O(1)
2
1
69(5)ꢁ], thus resulting in a zig-zag arrangement in the
Fig. 2. Molecular structure of Ph
2 6 4
P(O)CH(OH)C H OH-o (9) with
lattice as shown in Fig. 3(b).
The reaction of Ph PN(H)Ph with benzophenone
the atom-numbering scheme.
2
˚
from 1.486(2) to 1.495(4) A and the P–C bond distances
afforded tetraphenyl diphosphine monoxide Ph
Ph (12) through P–N bond cleavage as shown in
Scheme 3. The formation of product 12 was confirmed
PP(O)-
2
˚
are in the range of 1.785(5)–1.829(3) A.
The reactions of the corresponding aminobis(phos-
2
n
phines), PrN(PPh ) with aldehydes in a 1:2 ratio pro-
2
2
ceeds in a similar way as described earlier [7b] to give
the corresponding a-hydroxy phosphine oxides through
P(III)–N bond cleavage, except furfural. The reaction of
n
furfural with the n-butyl derivative, BuN(PPh ) , leads
2
2
to the P(III)–N bond cleavage product, Ph P(O)CH-
2
(
P–N insertion product, PrN{CH(C H O)P(O)Ph } .
C H O)OH, whereas the n-propyl derivative gives the
4 3
n
4
3
2 2
2
.1. Reactions of aminophosphines with ketones
The reactions of aminophosphines and amin-
obis(phosphines) with aldehydes led to the isolation of
either P(III)–N bond inserted products or a-hydroxy-
phosphine oxides via P(III)–N bond cleavage. In order
to get more insight into the reactivity of P(III)–N bonds,
similar reactions with ketones were carried out with
N-phenyldiphenylphosphinous amide, Ph PN(H)Ph as
2
a representative example.
The reactions of Ph PN(H)Ph with aliphatic ketones
2
such as 2-butanone, 4-methyl-2-pentanone and 4-hydro-
xy acetophenone yielded only the phosphine oxide,
2
Fig. 3. (a) Molecular structure of Ph P(O)N(H)Ph (11) with the atom-
numbering scheme. (b) Intermolecular hydrogen bonding interaction
of P@O of one molecule with N–H of an adjacent molecule in a zig-zag
arrangement (view down crystallographic axis a).
Table 3
˚
Selected bond distances (A) and bond angles (ꢁ) of 9
Bond distances
P(1)–O(1)
P(1)–C(7)
P(2)–O(4)
P(2)–C(26)
1.498(4)
1.785(5)
1.495(4)
1.790(5)
P(1)–C(1)
P(1)–C(13)
P(2)–C(20)
P(2)–C(32)
1.818(5)
1.827(7)
1.794(8)
1.829(6)
Table 4
˚
Selected bond distances (A) and bond angles (ꢁ) for 11
Bond distances
Bond angles
P(1)–O(1)
P(1)–C(7)
P(1)–N(1)
1.481(4)
1.798(5)
1.642(5)
P(1)–C(1)
N(1)–C(13)
1.794(5)
1.406(6)
O(1)–P(1)–C(1)
O(1)–P(1)–C(13)
C(1)–P(1)–C(13)
P(1)–C(13)–O(2)
O(2)–C(13)–C(14)
O(4)–P(2)–C(32)
C(20)–P(2)–C(32)
C(20)–P(2)–C(26)
P(2)–C(32)–O(5)
112.1(3)
O(1)–P(1)–C(7)
C(1)–P(1)–C(7)
C(7)–P(1)–C(13)
P(1)–C(13)–C(14)
O(4)–P(2)–C(26)
O(4)–P(2)–C(20)
C(26)–P(2)–C(32)
P(2)–C(32)–O(33)
O(5)–C(32)–C(33)
112.7(3)
110.4(3)
106.6(3)
102.3(5)
112.3(5)
111.3(3)
106.8(3)
107.0(3)
103.0(4)
106.7(2)
108.0(3)
113.4(4)
113.7(3)
110.7(3)
106.9(3)
112.6(4)
112.5(2)
Bond angles
O(1)–P(1)–N(1)
O(1)–P(1)–C(7)
N(1)–P(1)–C(7)
P(1)–N(1)–C(13)
P(1)–N(1)–H(1N)
114.5(2)
O(1)–P(1)–C(1)
N(1)–P(1)–C(1)
P(1)–N(1)–C(13)
C(13)–N(1)–H(1N)
113.6(2)
109.4(2)
108.6(2)
127.0(4)
114(3)
102.6(2)
127.0(4)
119(3)

S. Priya et al. / Polyhedron 24 (2005) 1641–1650
1645
H
N
O
NEt with uranyl acetate in dichloromethane yielded
eight-coordinate complexes, trans-[UO (OAc) {(Ph -
Ph
PPh2 11
2
2
2
O
R = C H
P(O)CH N(H)Ph) -jO,jO}] (15) and trans-[UO (OAc) -
2 2 2 2
{(Ph P(O)CH ) NEt-jO,jO}] (16), respectively in good
2 2 2
2
5
CH CH(CH )
2
3
2
R
C H -OH-p
6
4
yields. The IR spectra of complexes 15 and 16 show
1
O
O
ꢀ
a low frequency shift for P@O (ꢁ15 cm ) compared
31
H
N
O
H
O
Me
Ph
Ph
Ph
Ph
Ph
PPh2
to the free ligands indicating the coordination to the
metal centre. The P NMR spectra of complexes 15
Ph
N
PPh2
Ph P
PPh2
2
O
O
12
and 16 show single resonances at 46.8 and 46.6 ppm,
which are considerably deshielded compared to the
free ligand values, with coordination shifts of 17.3
and 16.4 ppm, respectively.
1
4
O
P
1
3
Ph
OH
n
Ph
The reactions of (Ph P(O)CH ) N Pr with Th(NO ) Æ
2
2 2
3 4
Scheme 3.
5H O affords a 10-coordinate complex, [Th(NO ) {(Ph -
2 3 3 2
n
P(O)CH ) N Pr} ](NO ) (17). The P NMR spectrum
31
2
2
2
3
3
by P NMR spectral data, which shows two doublets at
1
of 17 shows a single resonance at 40.1 ppm with a coor-
1
dination shift of 11 ppm. The IR and H NMR spectral
36.7 and ꢀ21.7 ppm for the P(III) and P(V) centers,
respectively with a J coupling of 228 Hz. The reaction
1
PP
data and the micro-analytical data support the proposed
structure. The mass spectrum of 17 shows m/z at 1392
corresponding to the cation. Similarly the reaction of
of Ph PN(H)Ph with acetyl acetone lead to the forma-
2
tion of Ph P(O)OH (13) through P–N bond cleavage.
2
3
1
5
5
Compound 13 exhibits a single resonance in its
NMR spectrum at 29.6 ppm. When Ph PN(H)Ph was
treated with acetophenone, insertion of ꢀC(Me)Phꢁ into
the P–N bond takes place, to afford Ph P(O)C-
P
Ph P(O)CH((g -C H )Fe(g -C H ))N(H)Ph (6) with
2 5 4 5 5
2
Th(NO ) Æ 5H O in a 4:1 ratio affords a 10-coordinate
3 4 2
5 5
complex, [Th(NO ) {Ph P(O)CH((g -C H )Fe(g -C H ))-
3 3 2 5 4 5 5
31
2
N(H)Ph} ](NO ) (18). The P NMR spectrum of 18
4 3
(
Me)(Ph)N(H)Ph (14) in good yield (Scheme 3). The
1
shows two resonances at 23.9 and 28.2 ppm (broad)
whereas the free ligand resonates at ꢀ29.2 ppm. The
3
P NMR spectrum of 14 shows a single resonance at
9.9 ppm. The structural composition of 14 was further
1
IR and H NMR spectral data and the micro-analytical
2
1
supported by H NMR and mass spectral data and by
elemental analysis (Scheme 4).
data support the proposed structure. The mass spectrum
of 18 shows m/z at 1394 corresponding to the cation.
n
The reaction of (Ph P(O)CH ) N Pr with Gd(NO ) Æ
2
2 2
3 3
2
.2. Coordination chemistry
5H O affords an 8-coordinate complex, [Gd(NO ) {(Ph -
2 3 2 2
31
P(O)CH ) N Pr} ](NO ) (19). The P NMR spectrum
n
2
2
2
3
The phosphine oxides readily react with oxophilic
metals to give coordination complexes [13]. The
reactions of Ph P(O)CH N(H)Ph and (Ph P(O)CH ) -
of 19 shows a single resonance at 28.1 ppm. The mass
spectrum of 19 shows m/z at 1256 corresponding to
the cation.
2
2
2
2 2
O
N
O
O
NO3
Ph2
P
Ph2
P
O
O
N
O
O
O
Ph2
P
O
O
UO (OAc) .5H O
Pr
N
Th(NO
3
)
4
.5H
2
O
O
O
2
2
2
O
O
O
N Et
Th
U
P
O
2
Ph2
O
Pr N
P
Ph
O
P
O O
P
Ph2
O O
Ph
2
P
N
Ph
N
16
2
O
Pr
Gd(NO ) .5H O
3
3
2
1
7
O
N
O
Ph
P
O
Ph
P
2
2
O
O
NO3
Pr
N
N Pr
Gd
P
O
O
P
Ph
Ph
2
O
O
2
N
O
19
Scheme 4.

1646
S. Priya et al. / Polyhedron 24 (2005) 1641–1650
5
The reaction of two equivalents of Ph P(O)CH((g -
olet Impact 400 FT IR instrument in KBr disks.
2
5
C H )Fe(g -C H ))N(H)Ph (6) with Co(NO ) Æ 6H O
Microanalyses were performed on a Carlo Erba model
1112 elemental analyser. The FAB mass spectra were re-
corded on a JEOL SX 102/DA-6000 mass spectrometer/
Data system using Argon/Xenon (6 kV, 10 mA) as the
FAB gas. Melting points were recorded in capillary
tubes and are uncorrected.
5
4
5
4
3 2
2
gave a purple coloured octahedral complex, [Co(NO ) -
3
2
5
5
{
Ph P(O)CH((g -C H )Fe(g -C H ))NHPh} ] (20) in
2 5 4 5 5 2
31
good yield. The P NMR spectra of 20 shows a broad
peak around 39 ppm due to the paramagnetic nature
of the complex. IR and micro analytical data are consis-
tent with the proposed structure.
4
.1. 1,3-C H {N(H)PPh } (1)
6 4 2 2
3
. Conclusions
To a solution of m-phenylene diamine (1.0 g,
.24 mmol), Et N (1.87 g, 18.4 mmol) and 4-dimethyla-
9
minopyridine (0.038 g, 0.31 mmol) in THF (30 mL) at
3
The reactions of aminophosphines with aldehydes
give either P–N inserted products or P–N cleavage
products. P–N insertion reactions provide a new route
to phosphorus–carbon bond formation whereas P–N
cleavage reactions provide a-hydroxy phosphine oxi-
des which can serve as valuable synthons [14] in asym-
metric synthesis. Further, P–N inserted products can
be used as ligands with oxophilic metal centers. The
reactions of both aliphatic and aromatic aldehydes
0 ꢁC, was added dropwise a solution of Ph PCl (4.08 g,
2
18.4 mmol) in THF (20 mL). The reaction mixture was
stirred at room temperature for 4 h, the solution was
then filtered through celite and the filtrate was concen-
trated and cooled to give an analytically pure sample
of 1. Yield: 46% (2.02 g, 4.23 mmol), m.p.: 88–92 ꢁC.
Anal. Calc. for C H N P : C, 75.61; H, 5.50; N,
3
0
26
2 2
5.88. Found: C, 75.91; H, 5.39; N, 5.83%. FTIR (KBr
n
ꢀ1
1
with BuN(PPh ) lead to a-hydroxy phosphine oxides
disk) cm : mNH 3218 s. H NMR (CDCl ): d 7.21–
3
31 1
2
2
via P–N bond cleavage whereas the n-propyl deriva-
tive gives a P–N inserted product with furfural and
a-hydroxy derivatives with other aldehydes. It is ob-
served that these reactions mainly depend on the oxi-
dation state of the phosphorus center and not on the
acidic proton present on the nitrogen center. The reac-
tivity also depends on the nature of nitrogen substitu-
ents in the aminophosphines. Further investigations to
understand the influence of phosphorus substituents
on product formation are in progress in our labora-
tory. Also, this methodology can be adopted to obtain
mixed donor ligands which have potential applications
in homogeneous catalysis and also in asymmetric syn-
thesis [15].
7.55 (m, phenyl). P{ H} NMR (CDCl ): d 35.2 (s).
3
+
MS (HRMS): 476.16 (M ).
4.2. 1,3-C H {N(H)CH P(O)Ph } (2)
6
4
2
2 2
0
mixture of 1,3-N,N -bis(diphenylphosphino)-
A
diaminobenzene (0.20 g, 0.419 mmol) and paraformal-
dehyde (0.025 g, 0.839 mmol) in 7 mL of toluene was
heated under reflux conditions for 10 h and cooled to
room temperature. The solvent was removed under re-
duced pressure and the residue obtained was washed
with hexane (4 · 3 mL) and re-dissolved in a mixture
of CH Cl -hexane (2:1) to give the crystalline product
2
2
2. Yield: 72% (0.160 g, 0.298 mmol), m.p.: 133–136 ꢁC.
Anal. Calc. for C H N O P : C, 71.62; H, 5.64; N,
3
2
30
2
2 2
5
.22. Found: C, 71.92; H, 5.31; N, 5.25%. FTIR (KBr
ꢀ
1
1
4
. Experimental
disk) cm : mPO 1174 s. H NMR (CD Cl ): d 2.39 (s,
2 2
31 1
CH , 4H), 7.15–7.99 (m, phenyl, 24H). P{ H} NMR
2
+
All the solvents were purified by conventional pro-
cedures and distilled prior to use. PhN(H)PPh [16],
(CD Cl ): d 28.7 (s). MS (HRMS): 536.18 (M ).
2
2
2
n
RN(PPh2)2 ( Pr, Bu [17]) and 1,2-Ph PN(H)C H -
n
4.3. 1,2-C H NCH N(CH P(O)Ph ) (3)
6 4 2 2 2 2
2
6
4
N(H)PPh [18] were prepared according to the literature
2
0
mixture of 1,2-N,N -bis(diphenylphosphino)-
procedures. Ph P(O)CH N(H)Ph and [Ph P(O)CH ] -
2 2
A
2
2
2
n
N Pr were prepared as described in our previous report
7b]. 5-Bromo salicylaldehyde was prepared following
diaminobenzene S(0.20 g, 0.419 mmol) and paraformal-
dehyde (0.037 g, 1.257 mmol) in toluene (7 mL) was
refluxed for 10 h. From the cooled reaction mixture,
solvent was removed under reduced pressure and the
residue obtained was washed with hexane (4 · 3 mL)
and redissolved in a mixture of CH Cl -n-hexane (2:1)
[
the reported procedure [19], and all other aldehydes
were used after purification except ferrocene carboxalde-
hyde (Strem). Metal salts were purchased from Loba
Chemicals, India and used with out further purification.
2
2
1
31
The H and P NMR spectra were recorded using VXR
00 S and Bruker spectrometers; Me Si was used as an
to give the crystalline product 3. Yield: 52% (0.120 g,
0.219 mmol), m.p.: 169–172 ꢁC. Anal. Calc. for C -
3
internal standard for the H NMR and 85% H PO as
4
33
1
H N O P : C, 72.25; H, 5.51; N, 5.11. Found: C,
30
3
4
2
2 2
3
1
ꢀ1
external standard for the P NMR. Positive values indi-
cate downfield shifts. IR spectra were recorded on a Nic-
72.19; H, 5.31; N, 5.17%. FTIR (KBr disk) cm : mPO
1
1180 s. H NMR (CDCl ): d 3.82 (br s, P–CH –N,
3
2

S. Priya et al. / Polyhedron 24 (2005) 1641–1650
1647
2
4.41 (d, CH, J = 10.32 Hz, 2H), 7.43–7.89 (m, phe-
4
2
5
H), 4.96 (s, N–CH –N, 2H), 6.34–8.65 (m, phenyl,
2
PH
1
3
1
1
31
4H). P{ H} NMR (CDCl ): d 26.6 (s). MS (FAB):
nyl, 10H). P{ H} NMR (CDCl ): d 31.3 (s).
3
3
+
47.21 (M ꢀ 1).
4.9. Ph P(O)CH(OH)Ph (8)
2
4.4. General procedure for the preparation of Ph P(O)-
CH(R)NHPh (R = 5-Br-C H OH-o, ferrocenyl)
2
Yield: 51% (0.291 g, 0.944 mmol), m.p.: 164–166 ꢁC
6
3
(dec.). Anal. Calc. for C H O P: C, 74.01; H, 5.56.
Found: C, 73.86; H, 5.49%. FTIR (KBr disk) cm :
19 17 2
ꢀ
1
A mixture of Ph PN(H)Ph (0.40 g, 1.44 mmol) and
2
1
one equivalent of aldehyde, RCHO was stirred at
room temperature for 12 h. The resultant slurry was
subjected to a vacuum to remove any volatiles and
the residue obtained was washed with n-hexane
mOH 3388 s, mPO 1163 vs. H NMR (CDCl ): d 1.83 (br
3
2
s, OH, D O exchangeable), 5.48 (d, CH,
J
=
HH
2
3
1
1
5.24 Hz, 1H), 7.13–7.90 (m, phenyl, 15H). P{ H}
NMR (CDCl ): d 30.6 (s).
3
(
3 · 5 mL) and crystallized in a mixture of CH Cl -n-
2
2
hexane (2:1) at 0 ꢁC to give analytically pure products.
4.10. Ph P(O)CH(OH)C H OH-o (9)
6
2
4
4
.5. Ph P(O)CH(5-Br-C H OH-o)N(H)Ph (5)
2
Yield: 51% (0.311 g, 0.959 mmol), m.p.: 90–92 ꢁC.
Anal. Calc. for C H O P: C, 70.37; H, 5.28. Found:
6
4
1
9
17
3
ꢀ1
Yield: 61% (0.215 g, 0.450 mmol), m.p.: 183–188 ꢁC.
Anal. Calc. for C H NO BrP: C, 62.78; H, 4.43; N,
C, 70.25; H, 5.33%. FTIR (KBr disk) cm : mOH
1
3229 br s, mPO 1139 vs. H NMR (CDCl ): d 4.01
2
5
21
2
3
2
(br s, OH, D O exchangeable), 5.45 (d, CH, J
2
.93. Found: C, 62.79; H, 4.55; N, 2.83%. FTIR (KBr
=
PH
2
ꢀ1
disk) cm : mOH 3382 br s, mNH 3053 s, mPO 1150 vs.
5.86 Hz, 1H), 6.67–7.82 (m, phenyl, 14H), 9.65 (br s,
1
1
31
OH, D O exchangeable). P{ H} NMR (CDCl ): d
2 3
H NMR (CDCl ): d 4.68 (br s, NH, D O exchange-
3
2
2
able), 5.49 (dd, CH, J = 5.9 Hz, 1H), 6.60–7.79 (m,
37.4 (s).
.11. Ph P(O)CH(OH)(OC H ) (10)
PH
3
1
1
phenyl, 18H). P{ H} NMR (CDCl ): d 37.8 (s).
3
4
2
4
3
5
5
4
.6. Ph P(O)CH{(g -C H )Fe(g -C H )}N(H)Ph (6)
2
5
5
5
4
Yield: 77% (0.313 g, 1.050 mmol), m.p.: 148–151 ꢁC.
Anal. Calc. for C H O P: C, 68.45; H, 5.06. Found:
Yield: 66% (0.230 g, 0.500 mmol), m.p.: 175–178 ꢁC.
Anal. Calc. for C H NOPFe: C, 70.89; H, 5.33; N,
1
7
15
3
ꢀ1
C, 68.32; H, 4.93%. FTIR (KBr disk) cm : mOH 3380
2
9
26
1
2
.85. Found: C, 70.82; H, 5.36; N, 2.80%. FTIR (KBr
1
br s, mPO 1154 vs. H NMR (CDCl ): d 4.77 (br s, OH,
3
ꢀ
1
2
D O exchangeable), 5.59 (d, CH, J = 5.5 Hz, 1H),
disk) cm : mNH 3426 s, mPO 1173 vs. H NMR (CDCl ):
3
2
PH
d 3.90–4.98 (m, ferrocenyl, 9H), 5.01 (br s, CH, 1H),
6.23–6.29 (m, furfuryl, 2H), 7.18–7.88 (m, phenyl & fur-
31
3
1
1
1
6
.68–7.72 (m, phenyl, 15H). P{ H} NMR (CDCl ): d
furyl, 11H). P{ H} NMR (CDCl ): d 31.5 (s).
3
3
2
9.2 (s).
n
4
.7. General procedure for the reaction of BuN(PPh )
5. Reaction of aminophosphines with ketones
2
n
0 0
R = Pr,) with R CHO (R = Pr, Ph, OC H ,
4 3
n
(
C H OH-o)
6
5.1. Reaction of Ph PN(H)Ph with CH C(O)R
2
4
3
(
R = C H , CH CH(CH ) , C H OH-p)
2 5 2 3 2 6 4
n
A mixture of Ph PN( Bu)PPh (0.400 g, 0.94 mmol)
2
2
n
and two equivalents of aldehyde, RCHO (R = Pr, Ph,
A mixture of Ph PN(H)Ph (0.400 g, 1.44 mmol) and
2
OC H and C H OH-o) was stirred at room tempera-
4
CH C(O)R (1.44 mmol) in toluene (10 mL) was stirred
3
3
6
4
ture for 24 h. The resultant slurry was subjected to a
vacuum to remove any volatiles and the residue ob-
tained was washed with n-hexane (3 · 5 mL) and crystal-
lized in a mixture of CH Cl -n-hexane (2:1) at 0 ꢁC to
at room temperature for 10 h. The solution was evapo-
rated under reduced pressure and the residue obtained
was crystallized from a 1:1 mixture of CH Cl –petro-
2
2
leum ether at 0 ꢁC to give analytically pure
2
2
give analytically pure products.
Ph P(O)N(H)Ph (11). Yield: 47% (0.20 g, 0.682 mmol)
(for R = C H ); 55% (0.23 g, 0.784 mmol) (for
2
2 5
4
.8. Ph P(O)CH(OH)CH CH CH (7)
2
R = CH CH(CH ) ); 50% (0.21 g, 0.716 mmol) (for
2 3 2
2
2
3
R = C H OH-p), m.p.: ꢁ230 ꢁC (dec.). Anal. Calc.
6
4
Yield: 42% (0.215 g, 0.784 mmol), m.p.: 116–118 ꢁC.
Anal. Calc. for C H O P: C, 70.06; H, 6.98. Found:
for C H NOP: C, 73.70; H, 5.49; N, 4.78. Found: C,
18 16
ꢀ
1
73.63; H, 5.55; N, 4.59%. FTIR (KBr disk) cm : mNH
1
6
19
2
ꢀ1
1
C, 70.67; H, 6.87%. FTIR (KBr disk) cm : mOH 3207
3121 s, mPO 1183 vs. H NMR (CDCl ): d 4.39 (d, NH,
3
1
s, m
JHH = 6.32 Hz, 3H), 1.38 (m, CH , 2H), 1.65 (m,
1179 vs. H NMR (CDCl ): d 0.85 (t, CH ,
D O exchangeable, 1H), 6.70–7.13 (m, NPh, 5H),
31
PO
3
3
2
3
1
7.15–7.77 (m, PPh , 10H). P{ H} NMR (CDCl ): d
2 3
2
CH , 2H), 1.73 (br s, OH, D O exchangeable, 1H),
2
18.5 (s).
2

1648
S. Priya et al. / Polyhedron 24 (2005) 1641–1650
5
.2. Reaction of Ph PN(H)Ph with benzophenone
2
Found: C, 50.32; H, 4.16; N, 2.67%. FTIR (KBr disk)
ꢀ
1
1
cm : mNH 3291 s, mCO 1612 s, mPO 1138 s. H NMR
(CDCl ): d 0.73 (br s, CH , 6H), 4.51 (br s, CH , 4H),
A mixture of Ph PN(H)Ph (0.200 g, 0.7 mmol) and
2
3
3
2
3
1
1
benzophenone (0.131 g, 0.7 mmol) was heated to 75–
8
6.70–7.60 (m, phenyl, 30H). P{ H} NMR (CDCl ): d
3
0 ꢁC with stirring. The melt was cooled to room tem-
46.9 (s).
perature after 4 h and the volatiles were removed under
reduced pressure to give a white residue. The residue ob-
tained was crystallized from CH Cl –petroleum ether
5
.6. [UO (CH COO) {(Ph P(O)CH ) NEt}] (16)
2 3 2 2 2 2
2
2
(
Ph PP(O)Ph (12). Yield: 94% (0.131 g, 0.34 mmol),
2:1) mixture at 0 ꢁC to get analytically pure
A solution of EtN(CH P(O)Ph ) (0.056 g, 0.10
2
2 2
2
2
mmol) in CH Cl (10 mL) was added to UO (OAc)
2
2
2
2
m.p.: 152–154 ꢁC. Anal. Calc. for C H OP : C,
2
4
20
2
(
0.050 g, 0.10 mmol) also in CH Cl (10 mL) and the
2 2
31
1
4.62; H, 5.22. Found: C, 74.69; H, 5.33%. P{ H}
7
reaction mixture was stirred at room temperature for
h. The solvent was evaporated from the reaction mix-
1
NMR (CDCl ): d ꢀ21.7 (d), 36.7(d); J = 228.3 Hz.
3
PP
6
ture under reduced pressure and the residue obtained
was re-crystallized from EtOH–diethyl ether (1:1) at
5
.3. Reaction of Ph PN(H)Ph with acetylacetone
2
0
8
ꢁC to give an analytically pure sample of 16. Yield:
8% (0.091 g, 0.110 mmol), m.p.: 118–121 ꢁC (dec.).
To a solution of Ph PN(H)Ph (1.00 g, 3.60 mmol) in
2
toluene (10 mL) was added acetylacetone (0.360 g,
.60 mmol) also in toluene (5 mL) and the reaction mix-
ture was stirred at room temperature for 12 h. The solu-
tion was then concentrated to 3 mL, diluted with diethyl
ether (7 mL) and on storing the solution at room tem-
perature yielded an analytically pure sample identified
Anal. Calc. for C H NO P U: C, 44.61; H, 4.09; N
1
disk) cm : mPO 1148 s, mCO 1611 m. H NMR (CDCl ):
d 0.89 (m, CH , 6H), 1.25 (s, CH , 3H), 2.46 (m, CH ,
2
3
2
35
8 2
3
.63. Found: C, 43.92; H, 3.99; N, 1.51%. FTIR (KBr
ꢀ1
1
3
3
3
2
H), 4.07 (br s, P–CH –N, 4H), 7.26–9.92 (m, phenyl,
2
31
1
2
0H). P{ H} NMR (CDCl ): d 42.4 (s).
3
as Ph P(O)OH (13). Yield: 77% (0.590 g, 2.70 mmol),
2
ꢀ
1
m.p.: 170–172 ꢁC (dec.). FTIR (KBr disk) cm : mPO
n
5.7. [Th(NO ) {(Ph P(O)CH ) N Pr} ]NO (17)
1
3
3
2
2 2
2
3
1
181 s. H NMR (CDCl ): d 7.45–7.88 (m, phenyl).
3
3
1
1
P{ H} NMR (CDCl ): d 29.6 (s). MS (FAB): 218.67
3
n
+
M ).
A
solution of,
.350 mmol) in ethanol (5 mL) was added to a solution
of Th(NO ) Æ 5H O (0.1 g, 0.175 mmol) also in ethanol
PrN(CH P(O)Ph )
(0.170 g,
2
2 2
(
0
3
4
2
5
.4. Reaction of Ph PN(H)Ph with acetophenone
2
(10 mL). The clear solution was allowed to stir at room
temperature for 4 h, during which time, the product pre-
cipitated out, was filtered and dried. The product was
re-crystallized from CH Cl –diethylether (1:1) mixture.
To a solution of Ph PN(H)Ph (0.400 g, 1.44 mmol) in
2
toluene (10 mL), was added acetophenone (0.173 g,
.44 mmol) and the reaction mixture was allowed to stir
at room temperature for 12 h. The solution was then
concentrated to 3 mL, diluted with diethyl ether
2
2
1
Yield: 76% (0.195 g, 0.121 mmol), m.p.: 109–111 ꢁC
(
4
dec.). Anal. Calc. for C H N O P Th: C, 47.87; H,
.29; N, 5.78%. Found: C, 48.11; H, 4.19; N, 5.94%.
58 62 6 16 4
(
Ph P(O)C(CH )PhN(H)Ph (14). Yield: 46% (0.320 g,
10 mL) and cooled to 0 ꢁC to give analytically pure
ꢀ
1
1
FTIR (KBr disk) cm : mNO3 1529 vs, m 1138 vs. H
NMR (CDCl ): d 0.26 (t, CH , J = 7.00 Hz, 3H),
PO
2
3
3
3
3
HH
0
.660 mmol), m.p.: 156–158 ꢁC (dec.). Anal. Calc. for
0
N, 4H), 6.87–7.73 (m, phenyl, 20H). P{ H} NMR
.81(m, CH , 2H), 3.15 (m, CH , 2H), 3.97 (s, P–CH –
2 2 2
3
C H NOP Æ CH Cl : C, 67.23; H, 5.43; N, 2.90.
2
6
24
2
2
1
1
1
Found: C, 67.49; H, 5.24; N, 2.79%. H NMR (CDCl ):
3
+
(
CDCl ): d 40.1 (s). MS (FAB): 1392.4 (M ꢀ NO ).
3
3
d 1.25 (s, CH , 3H), 6.91–6.97 (m, phenyl, 5H), 7.10–7.92
3
3
1
1
(
m, phenyl, 15H). P{ H} NMR (CDCl ): d 29.9 (s).
3
+
MS (FAB): 395 (M ꢀ 2).
5.8. [Th(NO ) {Ph P(O)CH(C H FeC H )N(H)-
3 3 2 5 4 5 5
Ph} ]NO (18)
4
3
5
.5. [UO (CH COO) (Ph P(O)CH N(H)Ph) ] (15)
2
3
2
2
2
2
A solution of Ph P(O)CH N(H)C H FeC H (0.103 g,
5
2
2
5
4
5
Uranyl acetate (0.10 g, 0.23 mmol) in methanol
5 mL) was added to Ph P(O)CH N(H)Ph (0.146 g,
0.021 mmol) in CH Cl (5 mL) was added to a solution
2 2
(
of Th(NO ) Æ 5H O (0.03 g, 0.05 mmol) in ethanol
3 4 2
2
2
0
.47 mmol) also in methanol (5 mL) and the yellow solu-
(10 mL). The clear solution was allowed to stir at room
temperature for 4 h, during which time, the product pre-
cipitated out, was filtered and dried. The product was re-
crystallized from CH Cl –diethylether (1:1) mixture.
tion obtained was stirred at room temperature for 2 h.
The solvent was evaporated under reduced pressure
and the residue was washed with n-hexane (2 · 5 mL)
and dried to give the crystalline product 15. Yield:
7
Calc. for C H N O P U: C, 50.31; H, 4.22; N, 2.79.
2
2
Yield: 64% (0.082 g, 0.034 mmol), m.p.: 152–154 ꢁC.
Anal. Calc. for C N O P Fe Th Æ 3CH Cl : C,
52.93; H, 4.11; N, 4.15. Found: C, 52.74; H, 4.07; N,
7% (0.184 g, 0.180 mmol), m.p.: 72–74 ꢁC (dec.). Anal.
H
116 104
8
16
4
4
2
2
4
2
42
2
8 2

S. Priya et al. / Polyhedron 24 (2005) 1641–1650
1649
ꢀ
1
4
.13%. FTIR (KBr disk) cm : mNO3 1515 s, mPO 1138 vs.
parameters. All the hydrogen atoms were geometrically
fixed and allowed to refine using a riding model.
1
H NMR (CDCl ): signals are broad, so not incorpo-
3
rated and the P signal is also slightly broad in this case.
3
1
3
1
1
P{ H} NMR (CDCl ): d 23.9 (s). MS (FAB): 2382
3
+
(
M ꢀ 1 ꢀ NO ).
6. Supplementary material
3
n
.9. [Gd(NO ) {(Ph P(O)CH ) N Pr} ]NO (19)
5
Full details of data collection and structure refinement
have been deposited with Cambridge Crystallographic
Data Center, CCDC reference numbers 245668, 245669
and 245670 for compounds 4, 9 and 11, respectively.
Copies of this information can be obtained free of charge
from the Director, CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (fax: +44-1223-336033; e-mail: deposit
@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).
3
2
2
2 2
2
3
n
A solution of the dioxide, PrN(CH P(O)Ph )
2
2 2
(
0.225 g, 0.460 mmol) in CH Cl (5 mL) was added to
2 2
a solution of Gd(NO ) Æ 5H O (0.1 g, 0.230 mmol) also
3
3
2
in ethanol (10 mL). The clear solution was allowed to
stir at room temperature for 4 h, during which time,
the product precipitated out, was filtered and dried.
The product was washed with diethylether and re-crys-
tallized from MeOH–CH Cl (1:1) mixture. Yield: 84%
2
2
(
0.256 g, 0.194 mmol), m.p.: 110–114 ꢁC (dec.). Anal.
Acknowledgements
Calc. for C H N O P Gd Æ CH Cl : C, 50.50; H,
5
8
62
5
13
4
2
2
4
.60; N, 4.99. Found: C, 50.37; H, 4.65; N, 4.86%. FTIR
ꢀ
We are grateful to the Department of Science and
Technology (DST) and CSIR, New Delhi, India for gen-
erous support. SP thanks CSIR, New Delhi, India for
JRF and SRF fellowships. The X-ray structural studies
were carried out at the National Single Crystal X-ray
Diffraction Facility, Indian Institute of Technology,
Bombay. We also thank RSIC, Mumbai, Sophisticated
Instrumentation Facility (SIF), Bangalore, for the spec-
tral facility. The refereesꢁ suggestions at the revision
stage were very helpful.
1
1
(
(
KBr disk) cm : mNO3 1490 vs, mPO 1159 s. H NMR
DMSO-d ): d 0.29 (br s, CH , 3H), 1.78 (br s, CH ,
6
3
2
2
CH –N), 7.48–7.79 (br m, phenyl, 20H).
NMR (DMSO-d ): d 28.1 (br s). MS (FAB): 1256
H), 2.51 (br s, CH , 2H), 3.57 (br s, DMSO & P–
2
3
1 1
P{ H}
2
6
+
(
M ꢀ NO ).
3
5
5
.10. [Co(O NO) (Ph P(O)CH((g -C H )Fe-
2
2
2
5
4
5
(
g -C H ))N(H)Ph) ] (20)
5
5
2
To an ethanolic solution (5 mL) of Co(NO ) Æ 6H O
3
2
5
2
5
References
(
0.030 g, 0.10 mmol), Ph P(O)CH((g -C H )Fe(g -C H ))-
2 5 4 5 5
N(H)Ph (0.101 g, 0.20 mmol) also in ethanol (10 mL)
was added and the mixture was stirred for 2 h at
room temperature. The resultant brown solution was
evaporated to dryness and the residue was washed
with n-hexane (3 · 5 mL) to give the analytically pure
product 20. Yield: 92% (0.110 g, 0.094 mmol), m.p.:
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