Preparation and coordination chemistry of p-(xylylenediaminodiphenyl) phosphine

Article abstract of DOI:10.1016/j.poly.2004.09.012

Reaction of p-xylene diamine with two equivalents of Ph₂PCl in the presence of NEt₃, proceeds in thf to give p- (xylylenediaminodiphenyl) phosphine 1 in good yield. 1 was derivatised as the dichalcogenides Ph₂P(O)NHCH

Full text of DOI:10.1016/j.poly.2004.09.012

Polyhedron 23 (2004) 2569–2574
www.elsevier.com/locate/poly
Preparation and coordination chemistry of
p-(xylylenediaminodiphenyl) phosphine
*
Alexandra M.Z. Slawin, Joanne Wheatley, J. Derek Woollins
School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, UK
Received 17 June 2004; revised 10 September 2004; accepted 20 September 2004
Abstract
Reaction of p-xylene diamine with two equivalents of Ph2PCl in the presence of NEt3, proceeds in thf to give p-(xylylenediami-
nodiphenyl) phosphine 1 in good yield. 1 was derivatised as the dichalcogenides Ph2P(O)NHCH2(C6H4)CH2NHP(O)Ph2,
Ph2P(S)NHCH2(C6H4)CH2NHP(S)Ph2 and Ph2P(Se)NHCH2(C6H4)CH2NHP(Se)Ph2 and the structures of the latter two com-
pounds determined crystallographically. The binuclear compounds [{(PEt3)PtCl2(Ph2PNHCH2)}2C6H4] (5), [{(PPhMe2)
PtCl2(Ph2PNHCH2)}2C6H4] (6), [{IrCl2(g5-C5Me5)(Ph2PNHCH2)}2C6H4] (7) [{RhCl2(g5-C5Me5)(Ph2PNHCH2)}2C6H4] (8),
i
[{RuCl2(g6-p-MeC6H4 Pr)(Ph2PNHCH2)}2C6H4] (9), [{Pd(g3-C3H5)Cl(Ph2PNHCH2)}2C6H4] (10), [{RhCl(C8H12) (Ph2PNH-
CH2)}2C6H4] (11), [{AuCl(Ph2PNHCH2)}2C4H6] (12) have been prepared and characterised spectroscopically.
Ó 2004 Elsevier Ltd. All rights reserved.
Keywords: Ligand; Bidentate; Bridging; X-ray; Phosphine
Me
N
1. Introduction
H
N
PPh2
PEt2
Bridging ligands are of interest as they can form a
number of bi-, tri- and tetra-nuclear species. There are
a variety of different ligands that can have bridging
properties and these include o-, m- and p-derivatives
of benzene or pyridine. For example, Ph2PNHC
6H4PPh2 [1,2], (A), (Et2PN(Me)C6H4PEt2) [3], (B),
PPh2
PEt2
A
B
O
PPh2
and 1-(diphenylphosphany)naphtha-2-oxydiphenyl-
phosphane [4], (C)
PPh2
C
whilst 2,6-bis(diphenylphosphino)pyridine, ({Ph2P}2py),
an o-bidentate pyridine, has the potential to act as a tri-
dentate PNP ligand [5,6] and was shown to react with a
variety of platinum and palladium starting materials to
give four different complexes. Gaw et al. [7] recently re-
ported the preparation of the tetradentate (phos-
phine)amine 1,4-{(Ph2P)2NCH2}2C6H4. They used this
*
Corresponding author. Tel.: +441 334 463 869; fax: +441 334 463
384.
E-mail address: jdw3@st-and.ac.uk (J.D. Woollins).
0277-5387/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2004.09.012

2570
A.M.Z. Slawin et al. / Polyhedron 23 (2004) 2569–2574
ligand to form a binuclear complex containing two cis-
[Mo(CO)4] metal fragments.
Here, we report the preparation of a new phos-
phine p-(xylylenediamonodiphenyl)phosphine which
has the potential to act as a bidentate bridging ligand.
Illustrative coordination complexes have been
prepared.
2. Results and discussion
Reaction of p-xylene diamine with two equivalents of
Ph2PCl in the presence of NEt3, proceeds in thf to give 1
(Eq. (1)) in very good yield (89%) with dP 43.3 ppm. The
IR spectrum has bands at 3303, 1432 and 997 cmꢀ1 that
are assigned to mNH, mPPh and mPN, respectively, (mPPh
represents the mCC of the phosphine aromatic rings).
The mass spectrum gave the expected parent ion and
fragmentation pattern and microanalysis gave good
results.
Fig. 1. X-ray structure of p-Ph2P(S)NHCH2(C6H4)CH2NHP(S)Ph2
(3).
Table 1
H2N
+
NH2
˚
Selected bond lengths (A) and angles (°) for p-Ph2P(S)NHCH2(C6H4)-
P
Cl
CH2NHP(S)Ph2 (3) and p-Ph2P(Se)NHCH2(C6H4)CH2NHP(Se)Ph2
(4). The values in square brackets are for the second independent
molecule in 3
(3)
(4)
NEt3
H
H
Bond lengths
P(1)–N(2)
E(1)–P(1)
P
N
N P
1.654(3)[1.661(2)]
1.9523(11) [1.9568(11)]
1.471(4)[1.472(4)]
1.811(3)[1.811(3)]
1.812(3)[1.812(3)]
1.654(5)
2.1198(10)
1.485(7)
1.797(6)
1.817(6)
ð1Þ
N(2)–C(3)
P(1)–C(11)
P(1)–C(17)
E
Bond angles
H
H
N(2)–P(1)–C(11)
N(2)–P(1)–C(17)
C(11)–P(1)–C(17)
N(2)–P(1)–E(1)
C(11)–P(1)–E(1)
C(17)–P(1)–E(1)
P(1)–N(2)–H(2)
103.43(13)[103.53(13)]
101.72(13)[103.36(13)]
106.39(14)[109.18(14)]
117.60(10)[116.27(10)]
112.64(11)[111.87(11)]
113.74(10)
104.8(3)
104.0(3)
104.5(3)
116.79(19)
113.7(2)
111.8(2)
110(3)
E
N P
P
N
E
The oxide (2) Ph2P(O)NHCH2(C6H4)CH2NH-
P(O)Ph2 was easily prepared by addition of excess
aqueous hydrogen peroxide to 1 in thf whilst the sul-
fur (3) and selenide (4) analogues were prepared by
the addition of elemental S or Se to 1 in toluene.
The EI+ mass spectral data obtained for these chalco-
genides gave the expected parent ions and fragmenta-
tion patterns. 31P{1H} NMR showed single
resonances (CDCl3) at dP 24.5 and 60.5 ppm for the
oxide and sulfide and at dP 58.6 ppm with selenium
satellites 1J(31P–77Se) 756 Hz for 4 which is typical
for a P@Se group [8].
In the solid state the sulfur and selenide analogues,
although not isomorphous, are isostructural, (Fig. 1,
Table 1) both have a centre of symmetry; in 3 P(1)–
S(1) = 1.9523(11) and P(1)–N(2) = 1.654(3) A and in 4
˚
P(1)–N(2) = 1.654(5) A and the P(1)–Se(1) = 2.1198(10)
˚
A which are in the range for previously reported bond
lengths [8].
109.1(18)[111.3(19)]
A range of binuclear compounds were synthesised
(Eq. (2)); thus reaction of [{PtCl(l-Cl)(PEt3)}2] with 1
gives [{(PEt3)PtCl2(Ph2PNHCH2)}2C6H4] (5). The EI+
mass spectrum of (5) contains the expected parent ion
and fragmentation pattern and the complex displays
resonances with platinum satellites in the 31P{1H}
NMR spectrum (dPA 34.0 ppm, 1J{31PA–195Pt} 1984
Hz, dPX 7.5 ppm, 1J{31PX–195Pt} 1715 Hz 2J{31PA–31PX}
18 Hz). The IR spectrum has mNH at 3289 cmꢀ1, mPPh and
mPN at 1435 and 997 cmꢀ1, respectively, and two mPtCl
(symmetric and antisymmetric) bands at 340 and 310
cmꢀ1 suggesting a cis geometry at the metal. (6–9) were
prepared in a similar way and have comparable spectro-
scopic properties to 5 (Table 2) see Fig. 2.
˚

A.M.Z. Slawin et al. / Polyhedron 23 (2004) 2569–2574
2571
Table 2
Characterisation data for Ph2PNHCH2C6H4CH2NHPPh2 and its derivatives
31P-{1H} NMR
IR (cmꢀ1
)
Microanalysis % Fcalc
dp (ppm)
mPN
mNH
mPPh
mP@E
mMCl
C
H
N
Ph2PNHCH2C6H4CH2NHPPh2 Æ H2O (1)
Ph2P(O)NHCH2C6H4CH2NHP(O)Ph2 (2)
Ph2P(S)NHCH2C6H4CH2NHP(S)Ph2 (3)
Ph2P(Se)NHCH2C6H4CH2NHP(Se)Ph2 (4)a
[{(PEt3)PtCl(Ph2PNHCH2)}2C6H4] (5)
43.3
997
998
997
996
997
998
997
996
996
998
995
997
3303
3097
3180
3177
3289
3300
3309
3300
3367
3246
3289
3279
1432
1437
1437
1435
1435
1435
1434
1434
1434
1433
1434
1435
–
–
73.43 (73.55)
69.37 (69.31)
65.27 (67.59)
57.53 (58.02)
41.36 (41.52)
44.05 (43.92)
47.64 (48.00)
54.76 (54.86)
55.53 (55.92)
52.34 (52.44)
54.66 (54.37)
39.98 (39.65)
6.39 (6.17)
5.93 (5.82)
5.35 (5.32)
5.14 (4.56)
5.12 (4.75)
4.17 (3.99)
4.64 (4.65)
5.31 (5.33)
4.73 (5.23)
4.78 (4.63)
5.32 (5.21)
3.28 (3.12)
5.64 (5.36)
5.38 (5.05)
5.11 (4.93)
4.24 (4.23)
2.36 (2.20)
2.61 (2.13)
2.35 (2.15)
2.41 (2.45)
2.46 (2.51)
3.45 (3.22)
2.89 (2.59)
2.94 (2.89)
24.5
1357
–
60.5
625
–
58.6a
34.0, 7.5b
35.1, ꢀ14.2c
34.4
551
–
–
–
–
–
–
–
–
–
340, 310
334, 311
289, 268
282, 267
291, 281
276
[{(PPhMe2)PtCl(Ph2PNHCH2)}2C6H4] (6)
[{IrCl2(g5-C5Me5)(Ph2PNHCH2)}2C6H4] (7)
[{RhCl2(g5-C5Me5)(Ph2PNHCH2)}2C6H4] Æ 0.25CH2Cl2 (8)
66.4d
[{RuCl2(g6p-MeC6H4 Pr)(Ph2 PNHCH2)}2C6H4] (9)
61.1
i
[{Pd(g3-C3H5)Cl(Ph2PNHCH2)}2C6H4] (10)
[{RhCl(C8H12)(Ph2PNHCH2)}2 C6H4] Æ CH2 Cl2 (11)
[{AuCl(Ph2PNHCH2)}2C4H6] (12)
58.1
62.3e
279
61.1
323
a
1J{31P–77Se} 756 Hz.
b
1J{31PA–195Pt} 1984 Hz, 1J{31PX–195Pt} 1715 Hz, 2J{31PA–31PX} 18 Hz.
1J{31PA–195Pt} 1956 Hz, 1J{31PX–195Pt} 1820 Hz, 2J{31PA–31PX} 19 Hz.
1J{31P–103Rh} 148 Hz.
c
d
e
1J{31P–103Rh} 157 Hz.
m
NH, mPPh, mPN and mPdCl vibrations. The 31P NMR
(CDCl3) is a single peak at dP 58.1 ppm. Similarly,
complex (11) was prepared by reaction of [{Rh(l-
Cl)(cod)}2] and 1 (Eq. (3)).
H
H
N
P
N
P
ð3Þ
L
L
[MLCl]2
H
H
Cl
M
P
N
N
P
M
Fig. 2. The X-ray structure of p-Ph2P(Se)NHCH2(C6H4)CH2NHP-
(Se)Ph2 (4).
Cl
M=Pd L=allyl 10, L=Rh L = cod (cyclooctadiene) 11
H
H
P
N
N
P
Table 3
Details of the X-ray data collections and refinements
3
4
Empirical formula
M
C32H3N2P2S2
568.64
C32H3N2P2Se2
664.46
L
ð2Þ
L
[MLCl2]2
H
H
Cl
Crystal system
Space group
Unit cell dimensions
triclinic
ꢀ
monoclinic
P21/n
M
P N
N
P
M
Cl
P1
Cl
Cl
˚
a (A)
9.2393(13)
10.6234(17)
16.444(3)
92.828(3)
100.309(3)
112.799(3)
1451.3(4)
2
10.950(5)
10.964(5)
12.459(6)
90
M= Pt L = PEt3 5, L = PMe2Ph 6
M= Ir L= Cp* 7, M = Rh L= Cp* 8
M= Ru L= p-cymene 9
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
[(Pd(g3-C3H5)Cl(Ph2PNHCH2))2C6H4] (10) was pre-
pared (68%) from [{Pd(l-Cl)(g3-C3H5)}2] and 1 in
dichloromethane. The microanalysis obtained was satis-
factory for the suggested structure and EI+ mass spec-
tral data gave the expected parent ion and
fragmentation pattern. The IR spectrum has bands at
3246, 1433, 998, 276 cmꢀ1 that correspond to the
96.528(10)
90
3
˚
U (A )
1468.1(12)
2
2.620
Z
l (mmꢀ1
Reflections measured
Independent reflections
Final R1, xR2 [I > 2r(I)]
)
0.318
7413
6267
2100
4150
0.0402, 0.1035
0.0401, 0.0651

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A.M.Z. Slawin et al. / Polyhedron 23 (2004) 2569–2574
We also prepared a simple bimetallic gold complex
3.2. Ph2P(O)NHCH2C6H4CH2NHP(O)Ph2 (2)
12. It is clear from the above observations that 1 is read-
ily prepared and able to function as a bridging ligand,
but there is no evidence for 1 behaving as a bidentate
trans ligand (see Table 3).
AqueousHydrogen peroxide (30% w/w, 0.1 cm3, 0.9
mmol) was added drop wise to a suspension of
Ph2PNHCH2C6H4CH2NHPPh2 (223 mg, 0.4 mmol) in
thf (10 cm3) and the mixture was stirred for 30 min.
The solution was filtered through Celite to remove a
small amount of insoluble material and the solvent
was removed in vacuo to give viscous oil, which was dis-
solved in dichloromethane (0.5 cm3) before precipitating
a colourless solid upon addition of diethyl ether (6 cm3).
The product was collected by suction filtration and dried
3. Experimental
Unless otherwise stated, all reactions were carried
out under an oxygen-free nitrogen atmosphere using
standard Schlenk techniques. Diethyl ether and thf
were purified by reflux over sodium-benzophenone
and distillation under nitrogen. Dichloromethane was
heated to reflux over calcium hydride and distilled un-
der nitrogen. Toluene and hexane were heated to re-
flux over sodium and distilled under nitrogen. The
complexes [AuCl(tht)] (tht = tetrahydrothiophene)[9],
1
in vacuo. Yield 188 mg, 79%. H NMR (CDCl3): d 1.4
(m, 4H, CH2), 4.1 (br s, 2H, NH), 7.3–7.9 (m, 24H, aro-
matics) ppm. MS: m/z 559 [M + Na]+.
3.3. Ph2P(S)NHCH2C6H4CH2NHP(S)Ph2 (3)
Ph2PNHCH2C6H4CH2NHPPh2 (214 mg, 0.4 mmol)
and sulfur (27 mg, 0.8 mmol) were heated to reflux in
toluene (15 cm3) for 4 h. The reaction mixture was fil-
tered through Celite to remove any insoluble material
remaining befpre reducing the solvent to yield an off-
white solid that was washed with CHCl3 (5 cm3) and
[MCl2(cod)] (M = Pt or Pd; cod = cycloocta-1,5-
i
diene)[10,11],
[{RuCl(l-Cl)(g6-p-MeC6H4 Pr)}2][12],
[{Rh(l-Cl)(cod)}2][13], [{Pd(l-Cl)(g3-C3H5)}2] [{MCl
(l-Cl)(g5-C5Me5)}2] (M = Rh or Ir) [14] [{PtCl
(l-Cl)(PMe2Ph)}2][15] and [{PtCl(l-Cl)(PEt3)}2] [16]
were prepared using the literature procedures. Chlo-
rodiphenylphopshine was distilled prior to use. NEt3
1
dried in vacuo. Yield 106 mg, 44%. H NMR (CDCl3):
d 1.4 (m, 4H, CH2), 4.1 (d, 2H, 2J (31P–1H) 8 Hz,
NH), 7.2–8.0 (m, 24H, aromatics) ppm. MS: m/z 591
[M + Na]+.
t
(99% purity), BuOK (95% purity), H2O2 (30 wt% in
H2O), p-xylylene diamine and reagent grade KBr were
used without further purification. Infra-red spectra
were recorded as KBr discs in the range 4000–200
cmꢀ1 on a Perkin–Elmer 2000 FTIR/RAMAN spec-
trometer. 31P and 1H NMR spectra were recorded
on a Gemini 2000 spectrometer (operating at 121.4
3.4. Ph2P(Se)NHCH2C6H4CH2NHP(Se)Ph2 (4)
Ph2PNHCH2C6H4CH2NHPPh2 (198 mg, 0.4 mmol)
and grey selenium (62 mg, 0.8 mmol) were heated to re-
flux in toluene (10 cm3) for 5 h. The solvent was re-
moved in vacuo and the crude product was taken up
in CH2Cl2 (5 cm3) and filtered through Celite to remove
a trace of unreacted selenium. The filtrate was evapo-
rated to dryness to yield an off-white solid, which was
dried in vacuo overnight. Yield 189 mg, 73%. 1H
NMR (CDCl3): d 1.4 (m, 4H, CH2), 4.1 (d, 2H, 2J
(31P–1H) 8 Hz, NH), 7.2–8.0 (m, 24H, aromatics) ppm.
MS: m/z 681 [M + Na]+.
1
MHz for 31P and 300 MHz for H) or a JEOL DEL-
TA 270 and are referenced to 85% H3PO4 and tetra-
methylsilane,
respectively.
Microanalyses
were
performed by the St. Andrews University service and
mass spectra by the Swansea Mass Spectrometer
Service.
3.1. Ph2PNHCH2C6H4CH2NHPPh2 (1)
To a stirring solution of triethylamine (2.26 g, 22.29
mmol) in thf (100 cm3) at room temperature was added
a thf (50 cm3) solution of chlorodiphenylphosphine (4.92
g, 22.29 mmol) over 2 h and simultaneously a thf solu-
tion of p-xylylene diamine (1.52 g, 11.14 mmol) over 2
h. The stirring was continued for a further hour before
removing the colourless precipitate that had formed by
filtration and the solvent removed to yield a colourless
solid which was recrystallised from dichloromethane
and hexane to give the desired product as a fine colour-
less solid that was collected by suction filtration and
3.5. [{(PEt3)PtCl2(Ph2PNHCH2)}2C6H4] (5)
[{PtCl(l-Cl)(PEt3)}2](39 mg, 0.05 mmol) and ligand
(26 mg, 0.05 mmol) were dissolved in dichloromethane
(5 cm3) and stirred overnight. The reaction mixture
was filtered through Celite to remove any insoluble
material and then reduced to 0.5 cm3 before addition
of diethyl ether (10 cm3) to precipitate a colourless solid
that was isolated by filtration and dried in vacuo. Yield
1
45 mg, 69%. H (CDCl3) d 1.0 (m, 18H, CH3), 1.2 (m,
1
2
dried in vacuo. Yield 4.99 g, 89%. H (CDCl3) d 1.4
(m, 4H, CH2), 4.1 (br s, 2H, NH), 7.3–7.9 (m, 24H, aro-
matics). MS: m/z 504 [M]+.
12H, CH2), 1.4 (m, 4H, CH2N), 4.1 (d, 2H, J(31P–1H)
8 Hz, NH), 7.2–8.0 (m, 24H, aromatics) ppm. MS: m/z
1293 [M + Na]+, 1235 [M ꢀ Cl]+, 1200 [M ꢀ 2Cl]+.

A.M.Z. Slawin et al. / Polyhedron 23 (2004) 2569–2574
2573
1
3.6. [{(PPhMe2)PtCl2(Ph2PNHCH2)}2C6H4] (6)
mg, 72%. H (CDCl3) d 0.8 (m, 12H, CH3), 1.2 ( 6H,
CH3), 1.9 (m, 4H, CH2N), 2.5 (m, 2H, CH), 4.1 (d,
2H, 2J (31P–1H) 8 Hz, NH), 7.2–8.0 (m, 28H, aromatics)
ppm. MS: m/z 1139 [M + Na]+.
[{PtCl(l-Cl)(PMe2Ph)}2](41 mg, 0.05 mmol) and
Ph2PNHCH2C6H4CH2NHPPh2 (26 mg, 0.05 mmol)
were dissolved in dry CH2Cl2 (5 cm3) and stirred over-
night. The pale yellow solution formed was filtered
through Celite to remove any inorganic impurities be-
fore reducing the solvent volume to 0.5 cm3 and addi-
3.10. [{Pd(g3-C3H5)Cl(Ph2PNHCH2)}2C6H4]. (10)
[{Pd(l-Cl)(g3-C3H5)}2](61 mg, 0.2 mmol) and
Ph2PNHCH2C6H4CH2NHPPh2 (84 mg, 0.2 mmol) were
dissolved in dry CH2Cl2 (5 cm3) and stirred overnight.
The reaction mixture was filtered through Celite to re-
move any insoluble inorganic material before reducing
the solvent to 0.5 cm3 and addition of diethyl ether (10
cm3) to precipitate a yellow microcrystalline solid that
was isolated by suction filtration. Yield 98 mg, 68%.
1H (CDCl3) d 1.3 (m, 8H, CH2), 1.9 (m, 4H, CH2N),
tion of diethyl ether (10 cm3) to precipitate
a
colourless solid that was isolated by suction filtration
1
and dried in vacuo. Yield 40 mg, 60%. H (CDCl3) d
1.2 (m, 12H, CH3), 1.4 (m, 4H, CH2N), 4.1 (d, 2H,
2J(31P–1H) 8 Hz, NH), 7.2–8.0 (m, 34H, aromatics)
ppm. MS: m/z 1333 [M + Na]+, 1275 [M ꢀ Cl]+, 1239
[M ꢀ 2Cl]+.
2
3.7. [{(IrCl2g5-C5Me5)(Ph2PNHCH2)}2C6H4] (7)
2.5 (m, 2H, CH), 4.1 (d, 2H, J (31P–1H) 8 Hz, NH),
7.2–8.0 (m, 24H, aromatics) ppm. MS: m/z 835
[M ꢀ Cl]+.
[{IrCl(l-Cl)(5-gC5Me5)}2](50 mg, 0.06 mmol) and
Ph2PNHCH2C6H4CH2NHPPh2 (32 mg, 0.06 mmol)
were dissolved in dry CH2Cl2 (5 cm3) and stirred for 2
h. The orange solution was filtered through Celite to re-
move a small amount of insoluble material before reduc-
ing the volume to 0.5 cm3 and addition of diethyl ether
(20 cm3) to precipitate an orange solid that was isolated
3.11. [{RhCl(C8H12)(Ph2PNHCH2)}2C6H4] (11)
[{Rh(cod)Cl}2](49
mg,
0.1
mmol)
and
Ph2PNHCH2C6H4CH2NHPPh2 (50 mg, 0.1 mmol) were
dissolved in dry toluene (5 cm3) and stirred for 2 h. The
solution was filtered through Celite to remove a small
amount of insoluble material before reducing the vol-
ume to 0.5 cm3 and addition of hexane (20 cm3) to pre-
cipitate a yellow solid that was isolated by filtration and
dried in vacuo. Recryst from CH2Cl2/hexane. Yield 56
1
by filtration and dried in vacuo. Yield 60 mg, 73%. H
(CDCl3) d 1.3 (s, 30H, CH3), 1.5 (m, 4H, CH2N), 4.1
2
(d, 2H, J (31P–1H) 8 Hz, NH), 7.2–8.0 (m, 24 H, aro-
matics) ppm MS: m/z 1323 [M + Na]+, 1158 [M ꢀ 4Cl]+.
3.8. [{RhCl2(g5-C5Me5)(Ph2PNHCH2)}2C6H4] (8)
1
mg, 57%. H (CDCl3) d 1.8 (m, 24H, C8H12), 1.9 (m,
2
4H, CH2N), 4.1 (d, 2H, J(31P–1H) 8dz, NH), 7.2–8.0
[{RhCl(l-Cl)(g5-C5Me5)}2](48 mg, 0.08 mmol) and
Ph2PNHCH2C6H4CH2NHPPh2 (39 mg, 0.08 mmol)
were dissolved in dry CH2Cl2 (5 cm3) and stirred for 2
h. The orange solution was filtered through Celite to re-
move a small amount of insoluble material before reduc-
ing the volume to 0.5 cm3 and addition of diethyl ether
(10 cm3) to precipitate an orange solid that was isolated
(m, 24H, aromatics) ppm MS: m/z 961 [M ꢀ Cl]+.
3.12. [{AuCl(Ph2PNHCH2)}2C4H6] (12)
[AuCl(tht)] (116 mg, 0.4 mmol) was dissolved in dry
CH2Cl2 (5 cm3) and Ph2PNHCH2C6H4CH2NHPPh2
(91 mg, 0.2 mmol) was added in one portion before stir-
ring for 30 min. The colourless solution was filtered
through Celite to remove a small amount of insoluble
material before reducing the volume to 2 cm3 precipitate
a colourless solid that was isolated by suction filtration
1
by filtration and dried in vacuo. Yield 68 mg, 78%. H
(CDCl3) d 1.3 (s, 30H, CH3), 1.5 (m, 4H, CH2N), 4.1
(d, 2H, 2J(31P–1H) 8 Hz, NH), 7.2–8.0 (m, 24 H, aromat-
ics) ppm. MS: m/z 1145 [M + Na]+, 1087 [M ꢀ Cl]+,
1049 [M ꢀ 2Cl]+.
1
and dried in vacuo. Yield 88 mg, 43%. H (CDCl3) d
2
1.6 (s, 4H, CH2N), 4.2 (d, 2H, J(31P–1H) 10 Hz, NH),
3.9. [{RuCl2(g6-p-MeC6H4 Pr)(Ph2PNHCH2)}2C6H4]
7.2–8.0 (m, 24H, aromatics) ppm MS: m/z 991
[M + Na]+, 933 [M ꢀ Cl]+.
i
(9)
i
[{RuCl(l-Cl)(g6-p-MeC6H4 Pr)}2] (47 mg, 0.08
mmol) and Ph2PNHCH2C6H4CH2NHPPh2 (39 mg,
0.08 mmol) were dissolved in dry CH2Cl2 (5 cm3) and
stirred for 1 h. The orange solution was filtered through
Celite to remove a small amount of insoluble material
before reducing the volume to 0.5 cm3 and addition of
diethyl ether (10 cm3) to precipitate an orange solid that
was isolated by filtration and dried in vacuo. Yield 62
4. Crystallography
X-ray diffraction studies were performed at 125 K
using a Bruker SMART diffractometer with graphite-
monochromated Mo Ka radiation. The structures
were solved by direct methods, non-hydrogen atoms
were refined with anisotropic displacement parameters;

2574
A.M.Z. Slawin et al. / Polyhedron 23 (2004) 2569–2574
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hydrogen atoms bound to carbon were idealised, the
NH protons were located by a DF map. Structural
refinements were by the full-matrix least-squares method
on F2 using SHELXTL [17].
Full lists of structure refinement data, atomic coordi-
nates, bond lengths and angles, anisotropic displace-
ment parameters and hydrogen atom parameters have
been deposited as supplementary material, CCDC
Nos. 239833 and 239834 at the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK [fax: +44-1223-336033; e-mail: deposit@ccdc.-
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