Preparation and coordination chemistry of N-diallylaminodiphenylphosphine and N-allylaminobis(diphenyl)phosphine

Article abstract of DOI:10.1016/j.poly.2004.09.017

N-diallylaminodiphenylphosphine coordinates using P, N or CC whereas N-allylaminobis(diphenylphosphine)phosphine is a simple P donor. N-diallylaminodiphenylphosphine and N-allylaminobis(diphenyl)phosphine have been prepared by reaction of the appropriate amine with Ph₂PCl. The coordination chemistry of these phosphines has been studied with a range of metals [Pd, Pt, Rh, Ir, Au, Ru, Mo]. Whilst the majority of the complexes are simple bidentate P,P donors, in the case of N- diallylaminodiphenylphosphinecoordination can involve the CC group or the nitrogen centre.

Full text of DOI:10.1016/j.poly.2004.09.017

Polyhedron 23 (2004) 3125–3132
www.elsevier.com/locate/poly
Preparation and coordination chemistry of
N-diallylaminodiphenylphosphine and
N-allylaminobis(diphenyl)phosphine
*
Alexandra M.Z. Slawin, Heather L. Milton, Joanne Wheatley, J. Derek Woollins
School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, UK
Received 24 June 2004; accepted 23 September 2004
Abstract
N-diallylaminodiphenylphosphine and N-allylaminobis(diphenyl)phosphine have been prepared by reaction of the appropriate
amine with Ph2PCl. The coordination chemistry of these phosphines has been studied with a range of metals [Pd, Pt, Rh, Ir, Au,
Ru, Mo]. Whilst the majority of the complexes are simple bidentate P,P donors, in the case of N-diallylaminodiphenylphosphine-
coordination can involve the C@C group or the nitrogen centre.
ꢀ 2004 Elsevier Ltd. All rights reserved.
Keywords: Phosphine; Hemilabile; X-ray structure
PCy3
Pd
1. Introduction
[(tmeda)Pd(CH3)2]
Diallylamine has been used as a ligand in a variety of
interesting reactions. Due to the presence of the two-al-
lyl arms it can bind through one or both depending on
the metal present in the co-ordination reaction. Andreu
and co-workers [1] demonstrated this binding mode
when they reacted (tmeda)Pd(CH3)2 with diallylamine
and PR3. They used the prepared palladium(0) mono-
phosphine complexes as catalysts in Suzuki coupling
reactions and were shown to be efficient cross-coupling
catalysts for aryl chlorides and phenylboronic acid com-
pared with the traditional Pd(II)–PR3 catalysts previ-
ously used.
+
PCy3
N
H
N
H
ð1Þ
Wu et al. in 2001 [2] prepared carbene complexes by
reacting pentacarbonyl[3-(cyclopent-1-enyl)-1-ethoxy-2-
propyn-1-ylidene]tungsten with diallylamine. Diallylam-
ine may also bind through one of the allyl chains and
through the nitrogen atom [3]. Several studies [4–7]
showed that addition of the secondary amine was stereo-
and regioselective and the E isomer was obtained. Baya
et al. [8] reported the reaction of [OsH(g5-
C5H5)Cl(GePh3)(PiPr3)] with LiN(C3H5)2 and showed
that the product cyclopentadienyl group contains a nitro-
gen atom. Diallylamine has been shown to react with
Ni(II) complexes containing furanyl rings. Eilmes et al.
[9] prepared the di- and mono-substituted succinyl
*
Corresponding author. Tel.: +44 133 446 3869; fax: +44 133 446
3384.
E-mail address: jdw3@st-and.ac.uk (J.D. Woollins).
0277-5387/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2004.09.017

3126
A.M.Z. Slawin et al. / Polyhedron 23 (2004) 3125–3132
dichloride products of 5,14-dihydro-6,8,15,17-tetram-
ethyldibenzo[b,I][1,4,8,11]tetraazacyclotetradecine which
were subsequently reacted with the appropriate amine to
yieldthedesiredaminocomplexingoodyields. Theamino
complexes formed are explained in terms of nucleophillic
attack of the amine on the carbonyl carbon within the
meso substituents of the macrocycle. It is clear the the dial-
lylamine group is potentially capable of interesting
transformations.
We have an ongoing interest in hemilabile ligands [10–
14] and bis(diphenylphosphino)amines [15] are of interest
since they relate to the well known ligand bis(diph-
enylphosphino)methane, Ph2PCH2PPh2 (dppm) [16–18].
Coordination of dppm to metal centres can occur through
the lone pair of electrons at one or both of the phosphorus
centres as well as by deprotonation of the methylene(or
NH) group to form a tridentate ligand (see Fig. 1).
However, diphosphinoamines have received signifi-
cantly less attention [19,20] and we have a program
of study into the synthesis of P–N–P phosphines
[21–30]. Here we report the preparation new phos-
phine and disphosphine that contains the diallyl and
allyl group and have the potential to act as a hemila-
bile ligand. Selected coordination complexes have also
been prepared.
nium satellites 1J(31P–77Se) 756 Hz which is typical
for a P@Se group.
Reaction of [PtCl2(cod)] with Ph2PN(C3H5)2 gave
interesting results. Reaction of [PtCl2(cod)] with three
equivalents of Ph2PN(C3H5)2 gives [Pt{Ph2PN
(C3H5)2}3][Cl2] (5). The FAB mass spectrum of 5 con-
tains the expected parent ion and fragmentation pat-
tern and the complex exhibits three different
resonances (Fig. 2) with platinum satellites in the
31P{1H} NMR spectrum (d(PA) 83.7 ppm,
1J{31PA–195Pt}
4800
Hz;
d(PX)
74.5
ppm,
9 Hz,
1J{31PX–195Pt} 2052 Hz, 2J{31PA–31PX}
2J{31PX–31PY} 44 Hz; d(PY) 47.9 ppm, J{31PY–195Pt}
281 Hz) which indicates the presence of three phos-
phorus ligands around the platinum centre, and by
comparison of the chemicals shifts and coupling con-
stants we propose the structure shown in Eq. (2). If
the reaction was performed with a 2:1 ligand/metal
molar ratio, 31P{1H} NMR indicated the presence of
5 and another complex. Reaction of [PtCl2(cod)] with
one equivalent of Ph2PN(C3H5)2 gives the second
2
product
observed
in
the
2:1
reaction,
[PtCl2{Ph2PN(C3H5)2}] (6), in good yield (65%).
Microanalysis gave satisfactory results for the forma-
tion of the chelate complex and FAB mass spectral
analysis gives the expected parent ion and fragmenta-
tion pattern. The complex displays a single resonance
with platinum satellites in the 31P{1H} NMR spectrum
2. Results and discussion
1
(dP 701. ppm, J(31P–195Pt) 3491 Hz) and the IR spec-
Reaction of diallylamine with one equivalent of
Ph2PCl in the presence of NEt3 proceeds in thf to give
1 (Eq. (2), 83% yield), dP 64.3 ppm. In the IR spectrum
bands are observed at 1638, 1433 and 993 cmꢀ1, which
are assigned to mC@C, mPPh2 and mPN respectively. The
microanalysis gave satisfactory results.
The oxide (2) Ph2P(O)N(C3H5)2 was easily prepared
by addition of urea hydrogen peroxide to a dichloro-
methane solution of 1, whilst the sulfur (3) and seleno
(4) analogues were prepared by the addition of ele-
mental S or Se to the ligand in toluene. Satisfactory
microanalysis was obtained for the 4 though only
fairly satisfactory results were obtained for 3 and 4
possible due to difficulties in purifying the oily prod-
ucts formed and the EI+ mass spectral data gave the
expected parent ion and fragmentation patterns. The
31P{1H} NMR show single resonances (CDCl3) at dP
31.3 and 69.8 ppm for the oxide and sulfide respec-
tively. The seleno analogue exhibits a single 31P{1H}
NMR resonance (CDCl3) at dP 58.1 ppm with sele-
trum has mPPh2 and mPN vibrations at 1434 and 1010
cmꢀ1, respectively and two mPtCl bands at 317 and
295 cmꢀ1 which suggest a cis geometry. [PdCl2(cod)]
behaved slightly differently to [PtCl2(cod)]; a 2:1 ratio
reaction [ligand:metal] gave two products, however,
in the presence of three equivalents of 1 only the 2:1
complex, [PdCl2{Ph2PN(C3H5)2}2] (7) is obtained.
The 31P{1H} NMR of 7 has two signals [dP 109.2
H
H
X
X
X
Ph
Ph
Ph
2 P
M
P
2 P
M
P
Ph
2
2
Ph2 P
PPh2
M
M
Fig. 1. Coordination modes of dppm, dppa and their respective anions
(X@CH or N).
Fig. 2. 31P NMR from the crude the reaction of three equivalents of
Ph2PN(C3H5)2 with [PtCl2(cod)].

A.M.Z. Slawin et al. / Polyhedron 23 (2004) 3125–3132
3127
2+
2
N
Cl
PPh2
PPh2
Ph
P
2 Pt
N
N
[PtCl2(cod)]
Ph2P Cl
HN
Ph2P
N
5
Cl
2 Pt Cl
1
Ph
ð2Þ
P
N
E
6
Ph2P
E
N
E = O 2, S 3, Se 4
and 44.7 ppm, 2J{31PA–31PX} 18 Hz] indicating two
phosphorus environments within the complex. The
FAB mass spectrum gives the expected parent ion
and microanalysis is found to be fairly satisfactory.
The IR spectrum has bands at 1435 and 995 cmꢀ1 that
correspond to mPPh2 and mPN, respectively and two
mPdCl bands at 292 and 277 cmꢀ1. As might be antici-
pated, the reaction of one equivalent of Ph2PN(C3H5)2
with [PdCl2 (cod)] gives [PdCl2{Ph2PN(C3H5)2}] (8) in
good yield. The crystal structure of 8 (Fig. 3) shows
that the molecule is cis-square planar. The ligand is
bound to the palladium metal via phosphorus [P(1)–
The IR spectrum has bands at 1433, 990 and 251 cmꢀ1
that correspond to mPPh2 and mPN and mRhCl vibrations,
respectively.
˚
Pd(1) 2.2247(6) A] and one of the olefinic arms of
the ligand.
The reaction of [PtMe2(cod)] with one equivalent
1
of
gave the expected chelate complex,
[PtMe2{Ph2PN (C3H5)2} (9). The FAB mass spectral
data obtained gave the expected parent ion and in
the IR spectrum mC@C, mPPh2 and mPN vibrations were
observed at 1636, 1432 and 992 cmꢀ1, respectively.
The 31P{1H} NMR (CD2Cl2) showed a single reso-
nance with platinum satellites (dP 90.7 ppm,
1J{31P–195Pt} 1937 Hz).
Reaction of 1 with [Mo(CO)4(nbd)] gives [Mo
(CO)4{Ph2PN(C3H5)2}] (10) as a yellow solid. Mono-
i
dentate
(11) was prepared from [{RuCl(a-Cl)(g6-p-Me-
C6H4 Pr)2}2] and 1. [RhCl{Ph2PN(C3H5)2}] (12) was ob-
P-[RuCl2{Ph2PN(C3H5)2}(g6-p-MeC6H4 Pr)]
i
Fig. 3. The X-ray structure of [PdCl2{Ph2PN(C3H5)2}] (8), selected
˚
tained from [{Rh(a-Cl)(cod)}2]. The 31P{1H} NMR
(CDCl3) shows a two resonances with rhodium satellites
bond lengths (A) and angles (ꢁ) : Pd(1)–Cl(1) 2.2983(7), Pd(1)–Cl(2)
2.3641(7), Pd(1)–P(1) 2.2247(6), Pd(1)–C(15) 2.192(2), Pd(1)–C(16)
2.177(3), P(1)–N(13) 1.6719(19), N(13)–C(14) 1.465(3), N(13)–C(17)
1.466(3), C(15)–C(16) 1.361(4). P(1)–Pd(1)–Cl(1) 88.07(2), N(13)–P(1)–
M(1) 103.54(7), P(1)–M(1)–Cl(2) 178.67(20).
1
(d(PA) 115.5 ppm, J(31PA–103Rh) 154 Hz. d(PX) 84.7
ppm, 1J{31PX–103Rh} 114 Hz. 2J{31PA–31PX} 25 Hz).

3128
A.M.Z. Slawin et al. / Polyhedron 23 (2004) 3125–3132
N
Ph2
Rh P
P
Ph2
N
Cl
12
Reaction of allylamine with two equivalents of
Ph2PCl in the presence of NEt3 proceeds in thf to give
13 in good yield, dP 62.9 ppm. The IR spectrum has
bands observed at 1635, 1434 and 993 cmꢀ1, which are
assigned to mC@C, mPPh and mPN, respectively.
PPh2
N
NH2
+
Ph2P Cl
2
PPh2
Fig. 5. The X-ray structure of [RuCl2{(Ph2P)2N(C3H5)}2] (18).
Selected bond lengths and angles: Ru(1)–Cl(1) 2.4189(7), Ru(1)–P(2)
ð3Þ
Reaction of [MCl2(cod)] with (C3H5)N(PPh2)2 gives
[PtCl2{(C3H5)N(PPh2)2}] (M@Pt 14, Pd 15) in good
yield. The FAB+ mass spectrum showed the expected
parent ion and the complex has dP 19.1 ppm,
1J{31P–195Pt} 3296 Hz. The IR spectrum showed bands
at 1635, 1435, 995, 291 and 245 cmꢀ1, which are as-
signed to mC@C, mPPh, mPN and two mPtCl vibrations
respectively.
2.3585(8), Ru(1)–P(1) 2.3356(7), P(2)–N(1) 1.721(2), P(1)–N(1)
˚
A P(2)–Ru(1)–P(1) 69.10(3), P(2)–Ru(1)–Cl(1) 85.65(2),
1.710(2)
P(1)–Ru(1)–Cl(1) 89.65(2), P(2)–N(1)–P(1) 101.78(12)ꢁ.
(C3H5)}] (20) were all obtained. The crystal structure
of 18 (Fig. 5) reveals bidentate coordination [bite angle
P(2)–Pt(1)–P(1) 69.10(3)ꢁ].
This work clearly demonstrates the ability of allyl
The crystal structure of 14 (Fig. 4) shows that it is
approximately square planar at platinum. The bite angle
of the chelating phosphine is significantly lower than the
ideal 90ꢁ {P(2)–Pt(1)–P(1) 72.03(8)ꢁ}.
aminophosphines to bind using a variety of motifs.
3. Experimental
We prepared a number of other simple complexes of
13,
[{(C3H5)N(PPh2)2}(AuCl)2] (17), [RuCl2{(Ph2P)2N
thus
[Mo(CO)4{(Ph2P)2N(C3H5)}]
(16)
3.1. [Ph2PN(C3H5)2] (1)
(C3H5)}2]
(18),
[RhCl(a-Cl)(g5-C5Me5){(Ph2P)2N
Diallylamine (2.841 g, 29.2 mmol) and triethylamine
(3.107 g, 30.7 mmol) were added together in dry thf
(50 cm3). Chlorodiphenylphosphine (6.453 g, 29.2
mmol) in dry thf (50 cm3) was added dropwise with stir-
ring overnight. Triethylamine hydrochloride was re-
moved by filtration under nitrogen and the solvent
removed in vacuo to yield a colourless oil. Yield: 6.840
g, 83%. Microanalysis: Found (calculated for
C18H20NP): C, 74.47 (76.85); H, 7.79 (7.17); N, 4.72
(C3H5)}] (19) and [IrCl(a-Cl)(g5-C5Me5){(Ph2P)2N
(4.98)%. 31P{1H} NMR (CDCl3): 64.3 ppm. H NMR
1
(CDCl3) d 7.5 (m, 10 H, Ph), 5.65 (m, 2H, CH@CH2),
5.05 (m, 4H, CH2), 3.45 (m, 4H, CH2) ppm. IR (thin
film): 1638, 1433, 933 cmꢀ1
.
3.2. Ph2P(O)N(C3H5)2 (2)
Ph2PN(C3H5)2 (256 mg, 0.9 mmol) was dissolved in
CH2Cl2 (20 cm3) and cooled to 0 ꢁC before addition
of urea hydrogen peroxide (86 mg, 0.9 mmol) was added
and the reaction mixture was stirred overnight. The
product was extracted from the CH2Cl2 by addition of
distilled water, washed with CH2Cl2 (3 · 5 cm3), dried
Fig. 4. The X-ray structure of [PtCl2{(C3H5)N(PPh2)2}] (14). Selected
bond lengths and angles: Pt(1)–Cl(1),2.352(2), Pt(1)–Cl(2) 2.347(2),
Pt(1)–P(1) 2.201(2), Pt (1)–P(2) 2.197(2), P(1)–N(1) 1.696(7), P(2)–N(1)
˚
1.703(7) A, P(2)–Pt(1)–P(1) 72.10(8), P(2)–Pt(1)–Cl(1) 97.44(9), P(1)–
Pt(1)–Cl(2) 98.73(9), Cl(2)–Pt(1)–Cl(1) 91.78(9), P(2)–N(1)–P(1)
99.2(4)ꢁ.

A.M.Z. Slawin et al. / Polyhedron 23 (2004) 3125–3132
3129
over magnesium sulfate and evaporated to dryness to
yield a colourless oil. Yield: 254 mg, 94%. Microanaly-
sis: Found (calculated for C18H20NOP): C, 68.61
(72.71); H, 6.58 (6.78); N, 4.46 (4.71)%. 31P{1H} NMR
2J(31PY–31PX) 44 Hz. d(PY) 47.9 (d) ppm, 2J(31PY–195Pt)
281 Hz. 1H NMR (CDCl3) d 7.55 (m, 30H, Ph), 5.65 (m,
4H, CH@CH2), 5.05 (m, 2H, chelate CH@CH2), 4.85
(m, 8H, CH2), 4.45 (m, 4H, chelate CH2), 3.45 (m,
12H, CH2) ppm. FAB+ MS: m/z 1075 [M ꢀ Cl]+. IR
1
(CDCl3): 31.3 ppm. H (CDCl3) d 7.55 (m, 10H, Ph),
5.65 (m, 2H, CH@CH2), 5.05 (m, 4H, CH2), 3.45 (m,
(KBr disc): 1637, 1436, 997, 296 cmꢀ1
.
4H, CH2) ppm. EI+ MS: m/z 297 [M]+. IR (thin film):
1635, 1433, 1181, 992 cmꢀ1
.
3.6. [PtCl2{Ph2PN(C3H5)2}] (6)
3.3. Ph2P(S)N(C3H5)2 (3)
Ph2PN(C3H5)2 (197 mg, 0.7 mmol) in CH2Cl2 (5 cm3)
was added dropwise to a CH2Cl2 (5 cm3) solution of
[PtCl2(cod)] (262 mg, 0.7 mmol) over 2.5 h. The solvent
was reduced to 1 cm3 before addition of hexane (10 cm3)
to yield an off white sticky solid on reduction of solvent.
The sticky solid was subsequently dissolved in CH2Cl2
(0.5 cm3) before addition of petroleum ether (40–60)
(10 cm3) to yield a colourless solid that was isolated
by suction filtration. Yield: 248 mg, 65%. Microanalysis:
Found (calculated for C18H20NPPtCl2): C, 40.02
(39.50); H, 3.50 (3.68); N, 3.41 (2.56)%. 31P{1H} NMR
(CDCl3): 70.1 ppm 1J(31P–195Pt) 3491 Hz. 1H NMR
(CDCl3) d 7.6 (m, 10H, aromatic), 5.3 (m, 2H, CH),
5.1 (m, 2H, CH2), 4.7 (d, 1H, 3J{195Pt–1H} 54 Hz,
2J{31P–1H} 8 Hz, CH2), 4.1 (d, 1H,3J{195Pt–1H} 59
Ph2PN(C3H5)2 (766 mg, 2.7 mmol) and elemental sul-
fur (87 mg, 2.7 mmol) were dissolved in dry toluene (10
cm3) to yield a yellow solution which was stirred over-
night. The reaction mixture was cooled to room temper-
ature and the solvent removed before addition of
CH2Cl2 (2 cm3) and filtering through Celite to remove
any remaining inorganic solid. After removing the
CH2Cl2 colourless oil was yielded. Yield: 753 mg, 88%.
Microanalysis: Found (calculated for C18H20NPS): C,
66.03 (68.98); H, 7.48 (6. 43); N, 4.80 (4.47)%. 31P{1H}
NMR (CDCl3): 69.8 ppm. 1H NMR (CDCl3) d 7.55
(m, 10H, Ph), 5.65 (m, 2H, CH@CH2), 5.05 (m, 4H,
CH2), 3.45 (m, 4H, CH2) ppm. EI+: m/z 273 [M]+. IR
(thin film): 1638, 1434, 997, 689 cmꢀ1
.
Hz, J{31P–1H} 13 Hz, CH2) 3.5 (m, 4H, NCH2) ppm.
2
FAB+ MS: m/z 569 [M + Na]+, 547 [M + H]+, 511
[M ꢀ Cl]+, 474/6 [M ꢀ 2Cl]2+. IR (KBr disc): 1634,
3.4. Ph2P(Se)N(C3H5)2 (4)
1434, 1010, 317, 295 cmꢀ1
.
Ph2PN(C3H5)2 (235 mg, 1.0 mmol) and grey sele-
nium (77 mg, 1.0 mmol) were refluxed in dry toluene
(10 cm3) for 1 h before cooling to room temperature
and filtering through a Celite plug to remove any
insoluble material. The solvent was reduced to 1 cm3
to yield a colourless solid that was isolated by suction
filtration and dried in vacuo. Yield: 269 mg, 86%.
Microanalysis: Found (calculated for C18H20NPSe):
C, 59.93 (60.01); H, 6.80 (5.60); N, 4.28 (3.89)%.
31P{1H} NMR (CDCl3): 58.1 ppm 1J(31P–77Se) 756
3.7. [PdCl2{Ph2PN(C3H5)2}2] (7)
(Ph2P)2N(C3H5)2 (124 mg, 0.4 mmol) and
[PdCl2(cod)] (42 mg, 0.1 mmol) were dissolved in
CH2Cl2 (5 cm3) to yield an orange solution that was stir-
red for 30 min. The solvent was reduced to 1 cm3 before
precipitating a pale yellow solid upon addition of diethyl
ether (20 cm3) that was isolated by suction filtration.
Yield: 100 mg, 92%. Microanalysis: Found (calculated
for C36H40P2N2PdCl2): C, 57.56 (58.43); H, 5.22
(5.45); N, 3.40 (3.79)%. 31P{1H} NMR (CDCl3): d(PA)
1
Hz. H NMR (CDCl3) d 7.55 (m, 10H, Ph), 5.65 (m,
2H, CH@CH2), 5.05 (m, 4H, CH2), 3.45 (m, 4H,
CH2) ppm. EI+ MS: m/z 361 [M + H]+. IR (KBr disc):
109.2 ppm. d(PX) 44.7 ppm. J{31PA–31PX} 18 Hz. H
NMR (CDCl3) d 7.55 (m, 20H, Ph), 5.65 (m, 3H,
CH@CH2), 5.05 (m, 1H, chelate CH@CH2), 4.85 (m,
2
1
1636, 1435, 995, 573 cmꢀ1
.
3.5. [Pt{Ph2PN(C3H5)2}3][Clꢀ2 ] (5)
6H, CH ), 4.45 (m, 2H, chelate CH2), 3.45 (m, 8H,
2
CH2) ppm. FAB+ MS: m/z 704 [M ꢀ Cl]+, 667/8
Ph2PN(C3H5)2 (165 mg, 0.6 mmol) and [PtCl2(cod)]
(73 mg, 0.2 mmol) were dissolved in CH2Cl2 (5 cm3)
to yield a pale yellow solution that was stirred for 30
min. The solvent was reduced to 1 cm3 before precipitat-
ing a colourless solid upon addition of diethyl ether
(cm3) that was isolated by suction filtration. Yield: 140
mg, 64%. Microanalysis: Found (calculated for
C54H60P3N3PtCl2): C, 58.84 (58.43); H, 5.38 (5.45); N,
3.73 (3.79)%. 31P{1H} NMR (CDCl3): d(PA) 83.7 (d)
ppm, 1J(31PA–195Pt) 4800 Hz. d(PX) 74.5 ppm,
[M ꢀ 2Cl]2+. IR (KBr disc): 1638, 1435, 995, 292, 277
cmꢀ1
.
3.8. [PdCl2{Ph2PN(C3H5)2}] (8)
Ph2PN(C3H5)2 (111 mg, 0.4 mmol) in CH2Cl2 (5 cm3)
was added dropwise to CH2Cl2 (5 cm3) solution of
[PdCl2(cod)] (112 mg, 0.4 mmol). After stirring for 30
min the solvent was reduced in vacuo to 0.5 cm3 before
precipitating a yellow microcrystalline solid upon
addition of hexane (10 cm3) and isolation by suction
1J(31PX–195Pt) 2052 Hz. 2J(31PA–31PX)
9
Hz.

3130
A.M.Z. Slawin et al. / Polyhedron 23 (2004) 3125–3132
filtration. Yield: 164 mg, 91%. Microanalysis: Found
(calculated for C18H20PNPdCl2): C, 46.76 (47.14); H,
4.18 (4.40); N, 2.70 (3.05)%. 31P{1H} NMR (CDCl3):
101.3 ppm. 1H NMR (CDCl3) d 7.55 (m, 10H, Ph),
5.65 (m, 1H, CH@CH2), 5.05 (m, 1H, chelate
CH@CH2), 4.85 (m, 2H, CH2), 4.45 (m, 2H, chelate
CH2), 3.45 (m, 4H, CH2) ppm. FAB+ MS: m/z 422
[M ꢀ Cl]+, 386 [M ꢀ 2Cl]2+. IR (KBr disc): 1634,
The solvent was reduced to 1 cm3 before addition of
diethyl ether (10 cm3) to precipitate an orange solid that
was isolated by suction filtration. Yield: 118 mg, 92%.
Microanalysis: Found (calculated for C28H34PNRuCl2):
C, 57.33 (57.24); H, 5.65 (5.83); N, 2.21 (2.38)%.
1
31P{1H} NMR (CDCl3): 74.1 ppm. H NMR (CDCl3)
d 7.3 (m, 14H, aromatic), 5.9 (m, 2H, CH), 4.8 (m,
4H, CH2), 3.5 (m, 4H, NCH2), 2.7 (m, 1 H, CH), 1.9
(s, 3H, ArCH3), 1.2 (m, 6H, CH3) ppm. FAB+ MS: m/
z 552 [M ꢀ Cl]+, 515/7 [M ꢀ 2Cl]2+. IR (KBr disc):
1435, 999, 317, 290 cmꢀ1
.
3.9. [PtMe2{Ph2PN(C3H5)2}] (9)
1637, 1432, 994, 299, 278 cmꢀ1
.
Ph2PNH(C3H5)2 (96 mg, 0.3 mmol) in CH2Cl2 (5
cm3) was added dropwise to a CH2Cl2 (5 cm3) solution
of [PtMe2(cod)] (114 mg, 0.3 mmol) over 2.5 h. The
solvent was reduced to 1 cm3 before addition of hex-
ane (10 cm3) to yield an off white sticky solid on
reduction of solvent. The sticky solid was subsequently
dissolved in CH2Cl2 (0.5 cm3) before addition of
petroleum ether (40–60) (10 cm3) to yield a colourless
solid that was isolated by suction filtration. Yield: 92
mg, 53%. Microanalysis: Found (calculated for
C20H26NPPt) C, 46.90 (47.42); H, 4.46 (5.18); N,
2.35 (2.77)%. 31P{1H} NMR (CD2Cl2): 90.7 ppm
3.12. [RhCl{Ph2PN(C3H5)2}2] (12)
(Ph2P)N(C3H5)2 (148 mg, 0.5 mmol) and [{Rh(a-
Cl)(cod)}2] (65 mg, 0.1 mmol) were dissolved in CH2Cl2
(5 cm3) to yield a dark red solution. The solvent was re-
duced to 1 cm3 before addition of diethyl ether (10 cm3)
to precipitate an orange solid that was isolated by suc-
tion filtration. Yield: 88 mg, 96%. Microanalysis: Found
(calculated for C36H40P2N2RhCl): C, 61.00 (61.70); H,
6.12 (5.75); N, 3.83 (4.00) 31P{1H} NMR (CDCl3):
d(PA) 115.5 (d) ppm, 1J (31PA–103Rh) 154 Hz. d(PX)
1
2
84.7 (d) ppm, J(31PX–103Rh) 114 Hz. J(31PA–31PX) 25
1
1
1J(31P–195Pt) 1937 Hz. H NMR (CD2Cl2) d 7.55 (m,
Hz. H NMR (CDCl3) d 7.3 (m, 20H, aromatic), 5.9
(m, 4H, CH), 4.8 (m, 8H, CH2), 3.5 (m, 8H, NCH2)
10H, aromatic), 5.3 (m, 2H, CH), 5.1 (m, 2H, CH2),
4.7 (d, 1 H, 3J(195Pt–1H) 54 Hz, 2J{31P–1H} 8 Hz,
ppm. FAB+ MS: m/z 665 [M ꢀ Cl]+. IR (KBr disc):
2
CH2), 4.1 (d, 1H,3J{195Pt–1H} 59 Hz, J{31P–1H} 13
1638, 1433, 990, 251 cmꢀ1
.
Hz, CH2) 3.5 (m, 4H, NCH2) ppm. FAB+ MS: m/z
490 [M ꢀ Me]+, 476 [M ꢀ 2Me]2+. IR (KBr disc):
3.13. (Ph2P)2N(C3H5) (13)
1636, 1432, 992 cmꢀ1
.
Allylamine (2.319 g, 40.6 mmol) and triethylamine
(8.219 g, 81.2 mmol) were dissolved in thf (50 cm3).
Chlorodiphenylphosphine (17.922 g, 81.2 mmol) in
thf (50 cm3) was added dropwise with stirring over-
night to yield triethylamine hydrochloride that was
isolated by filtration. The solvent was removed in va-
cuo to yield a colourless solid that was dried in vacuo.
Yield: 13.434 g, 78%. Microanalysis: Found (calcu-
lated for C27H25P2N): C, 75.19 (76.22); H, 6.20
(5.92); N, 3.34 (3.29)%. 31P{1H} NMR (CDCl3): 62.9
ppm. 1H NMR (CDCl3) d 7.3 (m, 20H, aromatic),
5.3 (m, 1H, CH), 4.8 (m, 2H, CH2), 3.9 (m, 2H,
NCH2) ppm. EI+ MS: m/z 424 [M]+. IR (KBr disc):
3.10. [Mo(CO)4{Ph2PN(C3H5)2}] (10)
To a CH2Cl2 (10 cm3) solution of [Mo(CO)4(nbd)]
(184 mg, 0.6 mmol) was added dropwise a CH2Cl2
(10 cm3) solution of (Ph2P)N(C3H5)2 (172 mg, 0.6
mmol). After stirring for 30 min the solvent was re-
duced to 2 cm3 before addition of petroleum ether
(b.p. 40–60) (20 cm3) and storing overnight at ꢀ18
ꢁC. The yellow solid precipitated was isolated by filtra-
tion and dried in vacuo. Yield: 95 mg, 32%. Micro-
analysis: Found (calculated for C22H20PNO4Mo): C,
54.04 (54.00); H, 3.16 (4.12); N, 2.76 (2.86)%.
31P{1H} NMR (CDCl3): 116.2 ppm. 1H NMR
(CDCl3) d 7.3 (m, 10H, aromatic), 5.3 (m, 1H, CH),
5.0 (m, 2H, CH2), 4.7 (m, 1H, CH), 4.0 (m, 2H, che-
late CH2), 3.5 (m, 4H, NCH2) ppm. FAB+ MS: m/z
[M]+, [M ꢀ CO]+, [M ꢀ 2CO]+, [M ꢀ 3CO]+ 523
1635, 1434, 993 cmꢀ1
.
3.14. [PtCl2{(Ph2P)2N(C3H5)}] (14)
(Ph2P)2N(C3H5) (88 mg, 0.2 mmol) and
[PtCl2(cod)] (77 mg, 0.2 mmol) were dissolved in
CH2Cl2 (10 cm3) to yield a pale yellow solution that
was stirred for 30 min. The solvent was reduced to 1
cm3 before precipitating a colourless solid upon addi-
tion of diethyl ether (20 cm3) that was isolated by
suction filtration. Yield: 101 mg, 71%. Microanalysis:
Found (calculated for C27H25P2NPtCl2): C, 47.81
[M ꢀ 4CO]+. IR (KBr disc): 1893, 1434, 987 cmꢀ1
.
3.11. [RuCl2{Ph2PN(C3H5)2}(g6-p-MeC6H4 Pr)] (11)
i
(Ph2P)N(C3H5)2 (122 mg, 0.4 mmol) and [RuCl(a-
i
Cl)(g6-p-MeC6H4 Pr)2] (133 mg, 0.2 mmol) were dis-
solved in CH2Cl2 (5 cm3) to yield a dark red solution.

A.M.Z. Slawin et al. / Polyhedron 23 (2004) 3125–3132
3131
(46.90); H, 2.53 (3.64); N, 1.56 (2.03)%. 31P{1H}
3.18. [RuCl2{(Ph2P)2N(C3 H5)}2] (18)
NMR (CDCl3): 19.1 ppm, J(31P–195Pt) 3296 Hz. H
NMR (CDCl3) d 7.3 (m, 20H, aromatic), 5.3 (m,
1H, CH), 4.9 (m, 2H, CH2), 3.5 (m, 2H, NCH2)
ppm. FAB+ MS: m/z 713/4 [M + Na]+, 691 [M]+,
656 [M ꢀ Cl]+, 621 [M ꢀ 2Cl]2+. IR(KBr disc): 1635,
1
1
(Ph2P)2N(C3H5) (150 mg, 0.4 mmol) and [RuCl(a-
Cl)(g6-p-MeC6H4 Pr)2] (54 mg, 0.1 mmol) were dis-
i
solved in CH2Cl2 (5 cm3) to yield a dark red solution.
The solvent was reduced to 1 cm3 before addition of
diethyl ether (10 cm3) to precipitate a red solid that
was isolated by suction filtration. Yield: 57 mg, 63%.
Microanalysis: Found (calculated for C54H50P4N2
RuCl2) C 62.64 (63.41), H 5.39 (4.93), N 2.90 (2.74)%.
1435, 995, 302, 291 cmꢀ1
.
3.15. [PdCl2{(Ph2P)2N(C3H5)}] (15)
1
(Ph2P)2N(C3H5) (104 mg, 0.2 mmol) and [PdCl2(cod)]
(70 mg, 0.2 mmol) were dissolved in CH2Cl2 (10 cm3) to
yield an orange solution that was stirred for 30 min. The
solvent was reduced to 1 cm3 before precipitating a pale
yellow solid upon addition of diethyl ether (20 cm3) that
was isolated by suction filtration. Yield: 125 mg, 85%.
Microanalysis: Found (calculated for C27H25P2NPdCl2):
C, 52.65 (53.80); H, 4.11 (4.18); N, 2.15 (2.32)%.
31P{1H} NMR (CDCl3): 79.7 ppm. H NMR (CDCl3)
d 7.3 (m, 40H, aromatic), 5.9 (m, 2H, CH), 4.8 (m,
4H, CH2), 3.5 (m, 4H, NCH2) ppm. FAB+ MS: m/z
1022 [M]+, 987 [M ꢀ Cl]+, 951 [M ꢀ 2Cl]2+. IR (KBr
disc): 1637, 1434, 998, 289, 273 cmꢀ1
.
3.19. [RhCp*Cl2{(Ph2P)2N(C3H5)}] (19)
1
31P{1H} NMR (CDCl3): 33.1 ppm. H NMR (CDCl3)
(Ph2P)2N(C3H5) (67 mg, 0.2 mmol) and [{RhCl(a-
Cl)(g5-C5Me5)}2] (49 mg, 0.1 mmol) were dissolved in
CH2Cl2 (5 cm3) to yield a blood red solution. The sol-
vent was reduced to 0.5 cm3 before addition of diethyl
ether (20 cm3) to precipitate an orange solid that was
isolated by suction filtration. Yield: 97 mg, 84%. Micro-
analysis: Found (calculated for C37H40P2NR-
hCl2.0.25CH2Cl2): C, 58.71 (59.20); H, 5.36 (5.40); N,
1.90 (1.85)%. 31P{1H} NMR (CDCl3): 70.9 ppm,
1J{31P–103Rh} 120 Hz. 1H NMR (CDCl3) d 7.3 (m,
20H, aromatic), 5.5 (m, 1H, CH), 4.9 (m, 2H, CH2),
3.8 (m, 2H, NCH2), 1.6 (m, 15H, Cp*) ppm. FAB+
MS: m/z 733 [M]+, 698 [M ꢀ Cl]+. IR (KBr disc):
d 7.3 (m, 20 H, aromatic), 5.3 (m, 1H, CH), 4.9 (m,
2H, CH2), 3.6 (m, 2H, NCH2) ppm. FAB+ MS: m/z
568 [M ꢀ Cl]+, 531 [M ꢀ 2Cl]2+. IR(KBr disc): 1638,
1435, 995, 329, 286 cmꢀ1
.
3.16. [Mo(CO)4{(Ph2P)2N(C3H5)}] (16)
To a CH2Cl2 (10 cm3) solution of [Mo(CO)4(nbd)]
(100 mg, 0.3 mmol) was added dropwise a CH2Cl2
(10 cm3) solution of (Ph2P)2N(C3H5) (141 mg, 0.3
mmol). After stirring for 30 min the solvent was re-
duced to 2 cm3 before addition of petroleum ether
(b.p. 40–60) (20 cm3) and storing overnight at ꢀ18
ꢁC. The yellow solid precipitated was isolated by filtra-
tion and dried in vacuo. Yield: 127 mg, 60%. Micro-
analysis: Found (calculated for C31H25P2NO4Mo): C
58.44 (58.78), H 3.83 (3.98), N 2.18 (2.21)%. 31P{1H}
NMR (CDCl3): 92.1 ppm. 1H NMR (CDCl3) d 7.3
(m, 20H, aromatic), 5.3 (m, 1H, CH), 4.7 (m, 2H,
CH2), 3.5 (m, 2H, NCH2) ppm. FAB+ MS: m/z 635
[M]+, 579 [M ꢀ 2CO]+, 523 [M ꢀ 4CO]+. IR (KBr
1629, 1434, 997, 297, 273 cmꢀ1
.
3.20. [IrCp*Cl2{(Ph2P)2N(C3H5)}] (20)
(Ph2P)2N(C3H5) (54 mg, 0.1 mmol) and [{IrCl(a-
Cl)(g5-C5Me5)}2] (51 mg, 0.05 mmol) were dissolved in
CH2Cl2 (10 cm3) to yield a yellow solution. The solvent
was reduced to 0.5 cm3 before addition of diethyl ether
(20 cm3) to precipitate a yellow solid that was isolated
by suction filtration and dried in vacuo. Yield: 76 mg,
disc): 1887, 1434, 999 cmꢀ1
.
72%.
Microanalysis:
Found
(calculated
for
3.17. [{(C3H5)N(PPh2)2}(AuCl)2] (17)
C37H40P2NIrCl2.0.5CH2Cl2): C, 51.64 (51.99); H, 4.54
(4.77); N, 1.59 (1.62)%. 31P{1H} NMR (CDCl3): 37.3
1
(Ph2P)2N(C3H5) (21 mg, 0.05 mmol) and
[AuCl(tht)] (32 mg, 0.1 mmol) were dissolved in
CHCl3 (2 cm3) to yield a colourless solution. Diethyl
ether (15 cm3) was added to precipitate a colourless
solid that was isolated by suction filtration. Yield: 20
mg, 45%. Microanalysis: Found (calculated for
C27H25P2NAu2Cl2): C, 36.22 (36.43); H, 2.67 (2.83);
N, 1.55 (1.57)%. 31P{1H} NMR (CDCl3): 83.8 ppm.
1H NMR (CDCl3) d 7.3 (m, 20H, aromatic), 5.3 (m,
1H, CH), 4.8 (m, 2H, CH2), 3.9 (m, 2H, NCH2),
ppm. H NMR (CDCl3) d 7.3 (m, 20H, aromatic), 5.3
(m, 1H, CH), 4.8 (m, 2H, CH2), 3.9 (m, 2H, NCH2),
1.6 (m, 15H, Cp*) ppm. FAB+ MS: m/z 823 [M]+, 788
[M ꢀ Cl]+. IR (KBr disc): 1629, 1434, 997, 310, 304 cmꢀ1
.
4. Crystal data
Single crystal X-ray diffraction studies on crystals were
performed using a Bruker SMART diffractometer with
graphite-monochromated Mo Ka radiation (k =
ppm. FAB+ MS: m/z 853 [M ꢀ Cl]+, 819 [M ꢀ 2Cl]2+
.
IR (KBr disc): 1655, 1436, 997, 282 cmꢀ1
.
0.71073 A). The structures were solved by direct
˚

3132
A.M.Z. Slawin et al. / Polyhedron 23 (2004) 3125–3132
´
[6] J.M. Moreto, S. Ricart, K.-H. Dotz, E. Molins, Organometallics
20 (2001) 62.
methods, the non-hydrogen atoms were refined with
anisotropic displacement parameters; hydrogen atoms
were fixed. Structural refinements were by the full-matrix
[7] (a) R. Aumann, B. Jasper, M. Lage, B. Krebs, Chem. Ber. 127
(1994) 2475;
least-squares method on F2 using SHELXTL
.
8
(b) R. Aumann, B. Jasper, R. Frolich, Organometallics 14 (1995)
231.
C18H20Cl2NPPd,
M = 458.62,
Monoclinic,
a =
˚
[8] M. Baya, P. Crochet, M.A. Esteruelas, E. Onate, Organometallics
20 (2001) 240.
8.5139(2), b = 10.6276(2), c = 20.3072(1) A, b=
3
˚
90.214(1)ꢁ. U = 1837.4(1) A , T = 125 K, space group
[9] J. Eilmes, M. Ptaszek, K. Wozniak, Polyhedron 21 (2002) 7.
[10] S.M. Aucott, M.L. Clarke, A.M.Z. Slawin, J.D. Woollins, J.
Chem. Soc. Dalton Trans. (2001) 972.
P21/c, Z = 4, 1(Mo Ka) = 1.386 mmꢀ1. Of 7708 meas-
ured data, 2624 were unique, to give R1[I > 2r(I)] =
0.0187, wR 0.0460. 14 C27H25NP2Cl2Pt, M = 691.41,
[11] S.M. Aucott, A.M.Z. Slawin, J.D. Woollins, J. Organomet.
Chem. 582 (1999) 83.
monoclinic, a = 10.8188(16), b = 14.661(2) c = 16.563(2)
3
[12] M.L. Clarke, A.M.Z. Slawin, M.V. Wheatley, J.D. Woollins, J.
Chem. Soc., Dalton Trans. (2001) 3421.
˚
˚
A, b = 94.512(2)ꢁ, U = 2618.9(7) A , space group P21/n
,
Z = 4, 1(Mo Ka) = 5.700 mmꢀ1. Of 12 794 measured
data, 3717 were unique to give R1[I > 2r(I)] = 0.0430
and wR2 = 0.1032. 18 C54H50N2P4Cl2Ru, M = 1022.81,
triclinic, a = 10.1826(17), b = 11.1207(19) c = 12.597(2)
[13] A.M.Z. Slawin, M. Wainwright, J.D. Woollins, New J. Chem. 24
(2000) 69.
[14] A.M.Z. Slawin, M. Wainwright, J.D. Woollins, J. Chem. Soc.
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˚
A, a = 111.490(3)ꢁ, b = 95.557(3)ꢁ, c = 113.376(3)ꢁ,
3
˚
U = 1168.3(3) A , space group P21/n, Z = 4, 1(Mo
Ka) = 0.627 mmꢀ1. Of 5901 measured data, 3306 were
unique to give R1[I > 2r(I)] = 0.0288 and wR2 = 0.0701.
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5. Supplementary material
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Crystallographic Data for the structural analyses has
been deposited with the Cambridge Crystallographic
data centre, CCDC Nos. 242186–242188. Copies of this
information may be obtained free of charge from The
Director CCDC, 12 Union Road, Cambridge, CB2
1EZ UK. (Fax: +44 1223 336-033 or E-mail deposit@
ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk.
[22] A.M.Z. Slawin, J.D. Woollins, Q. Zhang, Inorg. Chem. Comm. 2
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