Synthesis and structural characterization of hetero-binuclear complexes containing a Fe0→Mn+ bond bridged by a non-rigid P,N-phosphine ligand

Article abstract of DOI:10.1016/S0022-328X(00)00248-5

A new non-rigid phosphine ligand, N-(diphenylphosphinomethyl)morpholine (L), has been synthesized. Its reaction with K[HFe(CO)₄] results in the formation of the organometallic tridentate ligand trans-[Fe(CO)₃(μ-L)₂] which exhibits different coordinate modes in generating hetero-binuclear Fe⁰→Mⁿ⁺ complexes (M=Hg(II), Cd(II), Cu(I), Ag(I)). In the copper(I) complex, both tertiary amino groups coordinate to the Cu atom at Cu-N1=2.059(4) and Cu-N2=2.055(4) A?. In the cadmium(II) complex, one tertiary N atom coordinates to the Cd atom at Cd-N1=2.481(3) A?, but only a weak interaction of 2.730 A? exists between the Hg and a N atom in the isomorphous mercury(II) complex.

Full text of DOI:10.1016/S0022-328X(00)00248-5

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Journal of Organometallic Chemistry 605 (2000) 15–21
Synthesis and structural characterization of hetero-binuclear
complexes containing a Fe0“Mn+ bond bridged by a non-rigid
P,N-phosphine ligand
Hai-Bin Song a, Quan-Ming Wang a, Zheng-Zhi Zhang b, Thomas C.W. Mak a,*
a Department of Chemistry, Chinese Uni6ersity of Hong Kong, Shatin, New Territories, Hong Kong
b State Key Laboratory of Elemento-Organic Chemistry, Nankai Uni6ersity, Tianjin, PR China
Received 24 February 2000; accepted 16 April 2000
Abstract
A new non-rigid phosphine ligand, N-(diphenylphosphinomethyl)morpholine (L), has been synthesized. Its reaction with
K[HFe(CO)4] results in the formation of the organometallic tridentate ligand trans-[Fe(CO)3(m-L)2] which exhibits different
coordinate modes in generating hetero-binuclear Fe0“Mn+ complexes (M=Hg(II), Cd(II), Cu(I), Ag(I)). In the copper(I)
,
complex, both tertiary amino groups coordinate to the Cu atom at CuꢀN1=2.059(4) and CuꢀN2=2.055(4) A. In the
,
cadmium(II) complex, one tertiary N atom coordinates to the Cd atom at CdꢀN1=2.481(3) A, but only a weak interaction of
,
2.730 A exists between the Hg and a N atom in the isomorphous mercury(II) complex. © 2000 Elsevier Science S.A. All rights
reserved.
Keywords: Phosphine; Iron(0); Hetero-binuclear complex; Polydentate ligand; Metalꢀmetal bond
1. Introduction
tates their unique reactivities and coordination modes.
However, the non-rigid ligands Ph2PCH2NPh2 and
Ph2PCH2NHPh only exhibit a monodentate P-coordi-
nation mode to form mononuclear Rh, Au, and Cu
complexes [4]. The reason they do not function as a
bidentated ligand is attributed to the nearly planar
configuration around the tertiary amino nitrogen
atom, which precludes its coordination to a metal
center, as revealed by the structures of Rh(Ph2PCH2-
NPh2)2(CO)Cl, Au[(Ph2PCH2NPh2)]2Cl and Cu[(Ph2-
PCH2NPh2)]2Cl [4]. In our previous work, we re-
placed the phenylamino or diphenylamino group by a
pyridyl piperazine ring to ensure that the proximal
In the past two decades, hereto- and homo-binu-
clear organometallic compounds containing
metalꢀmetal bond have been subjected to extensive
investigation owing to interest in their unique struc-
tures, reactivities and spectroscopic properties [1].
Hemilabile bridging ligands such as 2-(diphenylphos-
a
phino)pyridine
(L1)
and
2,6-bis(diphenylphos-
phino)pyridine (L2) [2] were used widely to bind
different mental atoms, as electronic differentiation [3]
associated with the hard and soft donor atoms dic-
tertiary amino nitrogen atom has
a
pyramidal
configuration in the resulting non-rigid P,N-phos-
phine ligand (L3) and reported the synthesis and
structure of its binuclear silver(I) and mononuclear
iron(0) complexes [5].
* Corresponding author. Tel.: +852-303-4926531; fax: +852-
26035057.
E-mail address: tcwmak@cuhk.edu.hk (T.C.W. Mak).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00248-5

16
H.-B. Song et al. / Journal of Organometallic Chemistry 605 (2000) 15–21
Reaction of 1 with MX2 (M=Cd, Hg; X=I) and
[M(MeCN)4]ClO4 (M=Ag, Cu) resulted in the forma-
tion of binuclear complexes 2–5 in moderate yields.
Compared to 1, the IR w(CO) spectra of these binuclear
complexes split into three peaks and shift to higher
frequencies, which are consistent with both a change in
stereochemistry and a decrease in electron density on
However, the polydentate organometallic ligand
trans-Fe(CO)3(L3)2 does not readily form hereto-binu-
clear complexes containing a Fe0“Mn+ bond because
the coordination ability of pyridine is stronger than
that of a tertiary amine. Therefore, we replaced the
pyridylpiperazine group in L3 by morpholine to form
N-(diphenylphosphinomethyl)morpholine (L), and then
used it to synthesize the new organometallic tridentate
ligand trans-Fe(CO)3(L)2, whose reactivity and hetero-
binuclear complexes with Group 11 and 12 metals are
reported here (Scheme 1).
2. Results and discussion
Heating a mixture of diphenylphosphine, morpholine
and paraformaldehyde in toluene in a manner similar
to that devised by Maier yielded a colorless solution [6],
from which L was obtained as colorless crystals after
evaporation and crystallization from ethanol. Com-
pared to (diphenylphosphino)(diphenylamino)methane,
this P,N-phosphine ligand has a pyramidal nitrogen
atom seated at the bridge head of the morpholine ring,
which can readily coordinate to a metal center with its
lone-pair electrons.
Scheme 1.
The reaction of L with Fe(CO)5 and KOH in reflux-
ing ethanol afforded a yellow precipitate formulated as
trans-Fe(CO)3(L)2. The IR spectrum showed intense
carbonyl absorption at 1880 cm−1, which implied that
the local symmetry about the Fe atom is near D3h. The
molecular structure of trans-Fe(CO)3(L)2 (1) is depicted
in Fig. 1 with the atom numbering scheme. Selected
bond lengths and angles are listed in Table 1. The
coordination environment about the iron atom may be
best described as an FeP2C3 trigonal bipyramid with
two phosphine ligands occupying axial positions and
three carbonyl groups lying on the equatorial plane.
The PꢀFeꢀP angle of 178.24(3)° is comparable to that
(174.2(1)°) in trans-Fe(CO)3(Ph2Ppym)2 [7] and that
(177.1(1)°) in trans-Fe(CO)3(Ph2Ppy)2 [1d]. The three
Fig. 1. Perspective view (35% thermal ellipsoids) of trans-[Fe(m-
L)2(CO)3] (1). In this and all other figures, the hydrogen atoms have
been omitted for clarity.
CꢀFeꢀC
angles
(123.25(15),
119.30(15),
and
117.45(15)°) are not far from the ideal value of 120°.

H.-B. Song et al. / Journal of Organometallic Chemistry 605 (2000) 15–21
17
Table 1
X-ray crystallographic data refinement parameters of the complexes
Complex
1
2·Et2O
3·Et2O
4·H2O
6
Formula
C37H40FeN2O5P2
710.5
Triclinic
C41H50FeHgI2N2O6P2 C41H50FeCdI2N2O6P2 C37H42ClCuFeN2O10P2 C17H21HgI3NO2P
Formula weight
Crystal system
Space group
Crystal size (mm)
1239.01
1150.82
891.51
883.61
Monoclinic
P21/c (no. 14)
0.64×0.58×0.40
14.814(4)
12.580(2)
24.847(4)
Monoclinic
P21/c (no. 14)
0.35×0.25×0.19
14.839(1)
12.5764(8)
24.8657(16)
Triclinic
Triclinic
(
(
(
P1 (no. 2)
P1 (no. 2)
P1 (no. 2)
0.30×0.20×0.20
10.4174(5)
11.4122(5)
16.4169(8)
83.323(1)
84.097(1)
67.244(1)
1784.03(14)
2
0.34×0.29×0.20
11.2142(13)
13.6807(16)
14.3070(17)
106.274(2)
107.670(2)
94.732(3)
1973.6(4)
2
0.30×0.15×0.15
9.9782(6)
10.4880(7)
11.7326(8)
78.787(1)
78.499(1)
82.836(1)
1175.49(13)
2
,
a (A)
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
91.225(14)
91.413(1)
3
,
U (A )
Z
4629.4(16)
4
4639.1(5)
4
Dcalc (g cm−3
F(000)
)
1.323
744
0.556
0.963
8408
0.0207
5004
376
1.778
2400
1.648
2272
1.500
920
2.496
800
v(Mo–Ka) (mm−1
Goodness-of-fit
Unique reflections
Rint
)
5.073
1.013
9091
0.0603
5617
2.215
0.949
11239
0.0332
7365
1.113
0.971
6903
0.0505
10.565
0.917
5543
0.0276
Observed reflections
Variables (p)
R1, wR2
4767
3505
448
448
441
203
[I\2|(I)] a
0.049, 0.1289
0.086, 0.1475
0.0569, 0.1113
0.1123, 0.1312
0.0358, 0.0961
0.0648, 0.1070
0.0673, 0.1819
0.0925, 0.1985
0.0449, 0.1004
0.0765, 0.1123
R1,wR2 (all data)
2
a R1=ꢀ(ꢁFoꢁ−ꢁFcꢁ/ꢀꢁFoꢁ. wR2 ={w[ꢀ(ꢁFoꢁ−ꢁFcꢁ)2]/ꢀꢁFoꢁ }1/2
.
the iron(0) atom. The 31P{1H}-NMR spectra of com-
plexes 2–5 at room temperature consist of a singlet,
which indicates that both P atoms remain chemically
equivalent. The change in l value also implies the
formation of binuclear complexes. For complex 2, cou-
pling of two bonds (31P–Fe–199Hg) is observed with
2JPꢀFeꢀHg=177 Hz, and comparable coupling constants
have been observed previously in related complexes
containing an FeꢀHg bond, for example: Fe(CO)3(m-
means only one nitrogen atom has a weak interaction
,
with the mercury atom (the distance of 2.730 A is
,
longer than those in the range of 2.26–2.56 A for
mercury–tertiary amine complexes [12]). In complex 3,
the Cd atom is four-coordinated with a FeꢀCd=
,
2.7369(6) A, which is comparable to those of the
Fe(0)“Cd(II) dative bond in related complexes:
Fe(CO)3(m-Ph2Ppym)2CdX2 (X=Cl, Br, I, SCN)
,
(2.701(1)–2.818(1) A) [13], Fe(CO)3(m-Ph2Ptaz)2CdI2
Ph2Ppy)HgI2,
2JPꢀFeꢀHg=190
Hz
[1d],
and
Hg[Fe(CO)3{Si(OMe)3}(dppm-p)]2 (173 Hz) [8]. For
complex 3, the magnitude of the 2J(31P–Fe–111Cd)
value is 93 Hz, which is comparable to those observed
in mer-[{(MeO)3Si}(CO)3Fe(m-Ph2Py)CdBr(4-pic)] (82
Hz), mer-[{(MeO)3Si}(CO)3Fe(m-Ph2Py)]2Cd (66 Hz)
[9], and Fe(CO)3(m-Ph2Ppy)CdCl2 (34 Hz) [1d].
ORTEP drawings with atom numbering for com-
pounds 2–4 are shown in Figs. 2–4, respectively. Se-
lected bond lengths and angles are listed in Table 2.
Complexes 2–4 display a distorted octahedral geometry
about the Fe atom, in which the FeP2 unit is nearly
linear with a P(1)ꢀFeꢀP(2) angle close to 180°, and
three CO moieties and M lie in a plane perpendicular to
the FeP2 axis. In complex 2, the Hg atom is only
three-coordinated with a FeꢀHg distance of 2.6596(13)
,
A, which is comparable to those of the Fe(0)“Hg(II)
dative bond in Fe(CO)3(m-Ph2Ppy)2Hg(SCN)2 (2.648(3)
,
,
A) [10], Fe(CO)3(m-Ph2Ppy)2HgI2 (2.678(2) A) [1d], and
,
Fe(CO)3(m-Ph-MePpy)2Hg(m-Cl)2HgCl2 (2.592(4) A)
Fig. 2. Perspective view (35% thermal ellipsoids) of [Fe(m-
L)2(CO)3HgI2] (2).
,
[11]. The HgꢀN distances are 2.730 and 3.753 A, which

18
H.-B. Song et al. / Journal of Organometallic Chemistry 605 (2000) 15–21
(135.0(2)°) [11]. That the coordination modes of the
two nitrogen atoms in 2–4 differ with different metal
cations may be explained by the Lewis acid–base con-
cept. The tertiary amino nitrogen atom is a hard base
whose coordinated ability decreases with increasing
softness of the Lewis acid (Hg(II)\Cd(II)\Cu(I))
(Fig. 5).
Complex 6 is a salt isolated from the mother liquor
of Fe(CO)3(m-L)2HgI2. The P atom of L is converted to
oxidation state +5 and the N atom becomes proto-
nated. The resulting centrosymmetric cationic moieties
are linked into cyclic dimers through normal NꢀH···O
,
hydrogen bonds of length N···O=2.706 A. The anionic
part consists of a centrosymmetric [Hg2I6]2− dimer
consolidated by two bridging iodide ions.
In summary, we have taken advantage of the coordi-
nation ability of the tertiary amino nitrogen atom of
the morpholine fragment in the non-rigid P,N-phos-
phine ligand L to induce selective coordination of the
new organometallic ligand trans-Fe(CO)3(m-L)2 toward
Group 11 and 12 metal ions in the formation of hetero-
binuclear Fe0“Mn+ complexes.
Fig. 3. Perspective view (35% thermal ellipsoids) of [Fe(m-
L)2(CO)3CdI2] (3).
3. Experimental
Unless otherwise stated, all reactions were performed
under a nitrogen atmosphere using standard Schlenk
techniques. The solvents were purified by standard
methods. Infrared spectra were recorded on a Shimadzu
435 spectrometer as KBr discs. The 31P{1H}-NMR
spectra were recorded on an AC-P200 spectrometer at
81.03 MHz using H3PO4 as the external standard and
CDCl3 as the solvent. The ligand L was prepared by a
procedure similar to that of L3 [5].
3.1. Synthetic procedure
3.1.1. trans-[Fe(CO)3(L)2] (1)
Fig. 4. Perspective view (35% thermal ellipsoids) of the [Fe(m-
L)2(CO)3Cu]+ cation in 4.
This compound was prepared by the published pro-
cedure for trans-[Fe(CO)3(m-Ph2Ppy)2] [10] and single
crystals were recrystallized from CH2Cl2–CH3OH.
(Yield 65%. Found: C, 62.50; H, 5.52; N, 3.72. Calc. for
C37H40N2O5P2Fe: C, 62.54; H, 5.67; N, 3.94%). IR
,
(Ph2Ptaz=2-diphenylphosphinothiazole) (2.812(1) A)
w(CO): 1880s cm−1
.
31P{1H}-NMR(CDCl3, 298 K):
,
[14]. The CdꢀN distances are 2.481(3) and 3.968 A,
indicating that only one nitrogen atom is coordinated
to the cadmium atom. Complex 4 consists of a packing
of hetero-binuclear cations, discrete perchlorate anions
and lattice water molecules. The FeꢀCu distance of
2.550(1) A falls within the range of 2.394–2.580 A
reported for polynuclear complexes containing an
FeꢀCu bond [15]. The Cu(I) atom exhibits three coordi-
nation, which is different from related four-coordinate
complexes: the N1ꢀCu1ꢀN2 angle of 154.36(16)° is
larger than those of [Fe(CO)3(m-Ph2Ppy)2Cu(Me2-
CO)]+ (123.6(4)°) and [Fe(CO)3(m-Ph2Ppy)2Cu(H2O)]+
l=66.18 ppm.
3.1.2. [Fe(v-L)2(CO)3HgI2] (2)
HgI2 (0.078 g, 0.17 mmol) was added to a solution of
1 (0.1 g, 0.14 mmol) in dichloromethane (30 cm3). The
mixture was stirred for 2 h at room temperature (r.t.).
The solution was filtered and the filtrate concentrated.
n-Hexane was added to give a yellow solid (0.14 g,
83%). (Found: C, 38.00; H, 3.76; N, 2.18. Calc. for
C39H40N2O5P2FeI2Hg: C, 38.15; H, 3.46; N, 2.40%). IR
,
,
w(CO): 2010m, 1970s cm−1 31P{1H}-NMR (CDCl3,
.

H.-B. Song et al. / Journal of Organometallic Chemistry 605 (2000) 15–21
Table 2 (Continued)
19
Table 2
,
Selected bond lengths (A) and angles (°) for the complexes
Cu(1)ꢀFe(1)ꢀC(1)
Cu(1)ꢀFe(1)ꢀC(3)
Cu(1)ꢀN(2)ꢀC(33)
C(2)ꢀFe(1)ꢀC(3)
P(1)ꢀFe(1)ꢀC(1)
P(1)ꢀFe(1)ꢀC(3)
P(2)ꢀFe(1)ꢀC(2)
P(1)ꢀFe(1)ꢀP(2)
N(1)ꢀCu(1)ꢀFe(1)
N(1)ꢀCu(1)ꢀC(1)
N(2)ꢀCu(1)ꢀC(1)
C(1)ꢀCu(1)ꢀC(3)
O(2)ꢀC(2)ꢀFe(1)
67.9(2)
67.7(2)
108.2(3)
112.3(3)
87.3(2)
89.2(2)
94.3(2)
171.29(6) N(1)ꢀCu(1)ꢀN(2)
103.0(1)
98.2(2)
Cu(1)ꢀFe(1)ꢀC(2) 179.9(2)
Cu(1)ꢀN(1)ꢀC(16) 109.5(3)
Complex 1
Fe(1)ꢀP(1)
Fe(1)ꢀC(1)
Fe(1)ꢀC(3)
2.2010(7) Fe(1)ꢀP(2)
1.771(3)
1.767(4)
2.2064(7)
1.772(3)
C(1)ꢀFe(1)ꢀC(2)
C(1)ꢀFe(1)ꢀC(3)
P(1)ꢀFe(1)ꢀC(2)
P(2)ꢀFe(1)ꢀC(1)
P(2)ꢀFe(1)ꢀC(3)
112.1(3)
135.6(3)
94.3(2)
88.3(2)
88.7(2)
154.4(2)
Fe(1)ꢀC(2)
P(1)ꢀFe(1)ꢀP(2)
C(2)ꢀFe(1)ꢀP(1)
C(1)ꢀFe(1)ꢀP(2)
C(3)ꢀFe(1)ꢀP(2)
C(1)ꢀFe(1)ꢀC(3)
C(1)ꢀFe(1)ꢀP(1)
C(3)ꢀFe(1)ꢀP(1)
C(2)ꢀFe(1)ꢀP(2)
O(1)ꢀC(1)ꢀFe(1)
O(3)ꢀC(3)ꢀFe(1)
178.24(3) C(1)ꢀFe(1)ꢀP(1)
91.49(9) C(3)ꢀFe(1)ꢀP(1)
91.14(9) C(2)ꢀFe(1)ꢀP(2)
87.53(9)
91.4(1)
90.16(9)
119.3(2)
117.5(2)
91.49(9)
91.14(9)
88.4(1)
N(2)ꢀCu(1)ꢀFe(1) 102.7(1)
88.4(1)
C(1)ꢀFe(1)ꢀC(2)
C(2)ꢀFe(1)ꢀC(3)
N(1)ꢀCu(1)ꢀC(3)
N(2)ꢀCu(1)ꢀC(3)
O(1)ꢀC(1)ꢀFe(1)
O(3)ꢀC(3)ꢀFe(1)
101.1(2)
97.6(2)
177.4(5)
177.4(5)
123.3(2)
101.4(2)
82.8(2)
179.4(5)
87.53(9) C(2)ꢀFe(1)ꢀP(1)
91.4(1) C(1)ꢀFe(1)ꢀP(2)
90.16(9) C(3)ꢀFe(1)ꢀP(2)
176.4(3)
177.0(3)
O(2)ꢀC(2)ꢀFe(1)
179.6(3)
Complex 6
Hg(1)ꢀI(1)
Hg(1)ꢀI(3)
I(2)ꢀHg(1)c1
I(1)ꢀHg(1)ꢀI(2)
I(2)ꢀHg(1)ꢀI(3)
2.6582(7) Hg(1)ꢀI(2)
2.7049(7) Hg(1)ꢀI(2)c1
2.9531(7) P(1)ꢀO(1)
2.9169(7)
2.9531(7)
1.488(5)
Complex 2·Et2O
Hg(1)ꢀFe(1)
Hg(1)ꢀI(2)
Fe(1)ꢀC(2)
Fe(1)ꢀP(1)
C(1)ꢀO(1)
2.665(1)
2.7907(7) Fe(1)ꢀC(1)
1.79(1)
2.276(3)
1.14(1)
1.14(1)
Hg(1)ꢀI(1)
2.7748(8)
1.803(9)
1.80(1)
2.273(3)
1.15(1)
109.76(2) I(1)ꢀHg(1)ꢀI(3)
124.03(3)
Fe(1)ꢀC(3)
Fe(1)ꢀP(2)
C(2)ꢀO(2)
106.06(2) I(1)ꢀHg(1)ꢀI(2)c1 105.25(2)
111.44(2) I(2)ꢀHg(1)ꢀI(2)c1 97.02(2)
82.98(2)
I(3)ꢀHg(1)ꢀI(2)c1
Hg(1)ꢀI(2)ꢀHg(1)c1
C(3)ꢀO(3)
Hg(1)ꢀFe(1)ꢀP(1)
Hg(1)ꢀFe(1)ꢀC
Hg(1)ꢀFe(1)ꢀC(3)
Fe(1)ꢀHg(1)ꢀI(2)
C(1)ꢀFe(1)ꢀC(2)
C(2)ꢀFe(1)ꢀC(3)
P(1)ꢀFe(1)ꢀC(2)
P(2)ꢀFe(1)ꢀC(1)
P(2)ꢀFe(1)ꢀC(3)
O(1)ꢀC(1)ꢀFe(1)
O(3)ꢀC(3)ꢀFe(1)
87.52(7) Hg(1)ꢀFe(1)ꢀP(2)
95.41(7)
79.2(3)
74.2(3)
Hg(1)ꢀFe(1)ꢀC(2) 174.7(3)
Fe(1)ꢀHg(1)ꢀI(1)
298 K): l=58.41 ppm. JHgꢀP=88.5 Hz. Recrystalliza-
tion of 2 in CHCl3–Et2O yielded yellow crystals of
2·Et2O for X-ray analysis.
126.45(3)
107.90(2)
153.0(4)
90.2(3)
93.0(3)
89.3(3)
122.12(3) I(1)ꢀHg(1)ꢀI(2)
103.5(4)
103.4(4)
87.9(3)
88.8(3)
89.3(3)
175.3(9)
175.5(9)
C(1)ꢀFe(1)ꢀC(3)
P(1)ꢀFe(1)ꢀC(1)
P(1)ꢀFe(1)ꢀC(3)
P(2)ꢀFe(1)ꢀC(2)
P(1)ꢀFe(1)ꢀP(2)
O(2)ꢀC(2)ꢀFe(1)
3.1.3. [Fe(v-L)2(CO)3CdI2] (3)
CdI2 (0.063 g, 0.17 mmol) was added to a solution of
1 (0.1 g, 0.14 mmol) in dichloromethane (15 cm3). The
mixture was stirred for 2 h at r.t. The solution was
filtered and the filtrate concentrated. Ether was added
to give yellow crystals of 3·Et2O (0.104 g, 65%).
(Found: C, 42.68; H, 4.35; N, 2.44. Calc. for
C41H50N2O6P2FeI2Cd: C, 42.79; H, 4.38; N, 2.43%). IR
176.7(1)
178.9(9)
Complex 3·Et2O
Cd(1)ꢀFe(1)
Cd(1)ꢀI(1)
2.7369(6) Cd(1)ꢀN(1)
2.7628(4) Cd(1)ꢀI(2)
2.481(3)
2.7698(4)
2.266(1)
1.784(4)
1.138(5)
1.144(5)
Fe(1)ꢀP(1)
2.261(1)
1.809(4)
1.794(4)
1.150(5)
Fe(1)ꢀP(2)
Fe(1)ꢀC(2)
C(1)ꢀO(1)
C(3)ꢀO(3)
.
w(CO): 2000m, 1958s, 1936s cm−1 31P{1H}-NMR
Fe(1)ꢀC(1)
Fe(1)ꢀC(3)
C(2)ꢀO(2)
(CDCl3, 298 K): l=58.64 ppm. JCdꢀP=93 Hz.
Cd(1)ꢀFe(1)ꢀP(1)
Cd(1)ꢀFe(1)ꢀC(1)
Cd(1)ꢀFe(1)ꢀC(3)
Fe(1)ꢀCd(1)ꢀI(1)
N(1)ꢀCd(1)ꢀFe(1)
N(1)ꢀCd(1)ꢀI(2)
C(1)ꢀFe(1)ꢀC(2)
C(2)ꢀFe(1)ꢀC(3)
P(1)ꢀFe(1)ꢀC(2)
P(2)ꢀFe(1)ꢀC(1)
P(2)ꢀFe(1)ꢀC(3)
O(1)ꢀC(1)ꢀFe(1)
O(3)ꢀC(3)ꢀFe(1)
84.61(3) Cd(1)ꢀFe(1)ꢀP(2)
98.99(3)
3.1.4. [Fe(v-L)2(CO)3Cu]ClO4 (4)
78.4(1)
72.2(1)
Cd(1)ꢀFe(1)ꢀC(2) 171.0(1)
Cd(1)ꢀN(1)ꢀC(16)
Cu[(CH3CN)4]ClO4 (0.056 g, 0.17 mmol) was added
to a solution of 1 (0.1 g, 0.14 mmol) in dichloro-
methane (10 cm3). The mixture was stirred for 2 h at
r.t. The solution was filtered and the filtrate concen-
trated. Ether was added to give yellow crystals of
4·H2O (0.090 g, 72%). (Found: C, 49.49; H, 4.58; N,
3.82. Calc. for C37H42N2O10P2FeClCu: C, 49.84; H,
99.7(2)
119.84(2)
113.47(7)
108.52(1)
149.8(2)
90.0(1)
94.2(1)
89.2(1)
175.90(4)
179.0(4)
122.65(2) Fe(1)ꢀCd(1)ꢀI(2)
92.97(7) N(1)ꢀCd(1)ꢀI(1)
93.87(7) I(1)ꢀCd(1)ꢀI(2)
105.8(2)
104.2(2)
87.4(1)
88.8(1)
88.9(1)
173.8(4)
174.7(4)
C(1)ꢀFe(1)ꢀC(3)
P(1)ꢀFe(1)ꢀC(1)
P(1)ꢀFe(1)ꢀC(3)
P(2)ꢀFe(1)ꢀC(2)
P(1)ꢀFe(1)ꢀP(2)
O(2)ꢀC(2)ꢀFe(1)
4.75; N, 3.14%). IR w(CO): 1980m, 1912s, 1865s cm−1
31P{1H}-NMR (CDCl3, 298 K): l=70.67 ppm.
.
3.1.5. [Fe(v-L)2(CO)3AgClO4] (5)
Complex 4·H2O
Cu(1)ꢀFe(1)
Fe(1)ꢀP(1)
Fe(1)ꢀC(1)
Fe(1)ꢀC(3)
C(2)ꢀO(2)
Ag[(CH3CN)4]ClO4 (0.064 g, 0.17 mmol) was added
to a solution of 1 (0.1 g, 0.14 mmol) in dichloro-
methane (10 cm3). The mixture was stirred for 20 min
at r.t. The solution was filtered and the filtrate concen-
trated. Ether was added to give yellow crystals of
5·H2O (0.076 g, 58%). (Found: C, 47.79; H, 5.17; N,
2.550(1)
2.214(1)
1.780(6)
1.789(6)
1.152(6)
Cu(1)ꢀN(2)
Fe(1)ꢀP(2)
Fe(1)ꢀC(2)
C(1)ꢀO(1)
C(3)ꢀO(3)
2.055(4)
2.214(1)
1.766(5)
1.143(7)
1.150(7)
Cu(1)ꢀFe(1)ꢀP(1)
85.54(4) Cu(1)ꢀFe(1)ꢀP(2)
85.84(4)

20
H.-B. Song et al. / Journal of Organometallic Chemistry 605 (2000) 15–21
Fig. 5. Perspective view (35% thermal ellipsoids) of the dimeric cationic and anionic species in compound 6. The NꢀH···O hydrogen bonds are
represented by broken lines.
3.14. Calc. for C37H42N2O10P2FeClAg: C, 47.49; H,
Acknowledgements
4.52; N, 2.99%). IR w(CO): 1990m, 1920s, 1885s cm−1
31P{1H}-NMR (CDCl3, 298 K): l=70.67 ppm.
.
This work is supported by Hong Kong Research
Grants Council Earmarked Grant ref. No. CUHK
4022/98P.
3.2. X-ray crystallography
Intensity data for complexes 1, 3·Et2O, 4·H2O and 6
were collected at 293 K on a Bruker Smart CCD 1000
diffractometer system using Mo–Ka radiation (u=
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The Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (fax: +44-1223-336033; e-mail: de-
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cam.ac.uk).
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