Preparation and coordination chemistry of n-allylaminophosphane

Article abstract of DOI:10.1002/ejic.200400447

Reaction of allylamine with 1 equiv. of Ph₂PCl in the presence of NEt₃, proceeds in THF to give (allylamino)phosphane 1. 1 has been coordinated as a monodentate P ligand with Au, Pd, Pt, Ru, Rh, Ir and as a bidentate P,allyl ligand to Pt. Reaction of KOtBu with [PtCl₂{Ph ₂PNH(C₃H₅)}₂] in methanol gives [Pt{Ph₂PNH(C₃H₈O)}₂]. The X-ray structures of 1.Se and four demonstrative monodentate complexes all reveal intramolecular N-H...Cl hydrogen bonding. The structure of [Pt{Ph ₂PNH(C₃H₈O)}₂] consists of an N-H...O hydrogen-bonded dimer in the solid state. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejic.200400447

FULL PAPER
Preparation and Coordination Chemistry of n-Allylaminophosphane
Alexandra M. Z. Slawin,[a] Joanne Wheatley,[a] and J. Derek Woollins*[a]
Keywords: Phosphanes / Alkenes / Hemilabile complexes / X-ray structures
Reaction of allylamine with 1 equiv. of Ph2PCl in the pres-
ence of NEt3, proceeds in THF to give (allylamino)phosphane
1. 1 has been coordinated as a monodentate P ligand with
Au, Pd, Pt, Ru, Rh, Ir and as a bidentate P,allyl ligand to Pt.
Reaction of KOtBu with [PtCl2{Ph2PNH(C3H5)}2] in methanol
gives [Pt{Ph2PNH(C3H8O)}2]. The X-ray structures of 1.Se
and four demonstrative monodentate complexes all reveal
intramolecular N–H···Cl hydrogen bonding. The structure of
[Pt{Ph2PNH(C3H8O)}2] consists of an N–H···O hydrogen-
bonded dimer in the solid state.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
irreversible depending on the small molecule that was used
in the reaction. A reversible reaction was observed when
acetonitrile was used; however, in the presence of CO the
reaction was found to be irreversible but in both instances
the DPVP ligand underwent an η3- to η1-shift that opened
up a coordination site on the metal centre. It is clear that
there is a potentially rich and diverse coordination chemis-
try available for phosphane–alkenes.
Here, we report the preparation of an aminophosphane
which contains an olefinic side chain and thus the potential
to act as a hemilabile ligand. Illustrative coordination com-
plexes have been prepared.
Introduction
Phosphane–alkenes have the potential to coordinate with
the phosphorus atom or through the olefin moiety. For ex-
ample, Coutinho et al.[1] treated a variety of phosphido-
bridged complexes, [(OC)4M(µ-PPh2)2RhH(CO)(PPh3)],
with the phosphanylalkenes Ph2P(CH2)nCH=CH2 (M = Cr,
Mo or W; n = 1–3); in these reactions the olefin undergoes
hydroformylation, which is of great interest today in com-
mercial processes including the Rhone-Poulenc/Ruhr
Chemie aqueous-based system.[2] Furthermore, work con-
tinues to prepare ligands that lead to greater regioselectivity
and/or enantioselectivity.[3] It is of interest to investigate
other potentially hemilabile ligands to increase the success
and efficiency of current processes and in early work the
olefinic fragment was used as a stabilising group with
strongly bonding phosphane ligands.[4] More recently the
study of phosphane–alkene ligands has focused on the
weakly ligating nature of the alkene, for example, Brookes[4]
displaced the olefinic groups of a rhodium complex with a
tetraphenylborate anion to yield a piano stool metal com-
plex. Lindner et al.[5] showed that the furan ring in (phopsh-
anylalkyl)furan ligands could ligate to metal centres in an
η1-fashion through the oxygen atom or by an η2-fashion
through the C=C double bonds. The most favoured coordi-
nation mode of these types of phosphane–alkene ligands
was shown to be the η2-fashion as the partial donation of
the lone pair from the oxygen atom makes the η1-fashion
coordination less favourable due to the oxygen atom being
a poorer σ-donor than the olefinic groups. Diphenyl(vinyl)
phosphane (DPVP) was shown by the Barthel-Rosa re-
search group to be a hemilabile ligand when coordiniated
to ruthenium(ii) centres.[5] They showed that the (η3-DPVP)
ruthenium(ii) complex could react both reversibly and
Results and Discussion
Reaction of allylamine with 1 equiv. of Ph2PCl in the
presence of NEt3, proceeds in THF to give 1 which was
isolated (41 % yield) by filtration from Et3NH+Cl– as a
colourless oil that was purified by distillation (132 °C/
0.2 Torr). After storing under nitrogen at –18 °C a colour-
less waxy solid formed (41 % yield). The 31P{1H} NMR
spectrum of 1 consists of a singlet at δP = 42.5 ppm. The
EI+ mass spectrum gave the expected fragmentation pattern
and parent ion observed at m/z 242. The microanalysis gave
satisfactory results for the suggested structure. The chalcog-
enides of Ph2PNH(C3H5) were prepared easily [Equation
(1)].
[a]
School of Chemistry, University of St Andrews,
St Andrews, Fife KY16 9ST
E-mail: jdw3@st-and.ac.uk
(1)
Eur. J. Inorg. Chem. 2005, 713–720
DOI: 10.1002/ejic.200400447
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
713

A. M. Z Slawin, J. Wheatley, J. D. Woollins
FULL PAPER
The oxide Ph2P(O)NH(C3H5) (2) was prepared by ad- [PtCl2(cod)] with
1
in
a
1:2 molar ratio gave
dition of urea/hydrogen peroxide to a dichloromethane [PtCl2{Ph2PNH(C3H5)}2] (6) in very good yield (90 %). The
solution of 1 whilst the sulfur and selenium analogues 3 FAB mass spectrum of 6 showed the expected parent ion
and 4 were prepared by the addition of elemental S or Se and fragmentation pattern and the complex displays a sin-
to the ligand in toluene. Microanalysis and EI+ mass spec- gle resonance with platinum satellites in the 31P{1H} NMR
1
troscopic data for all the chalcogenides prepared were satis- spectrum [δP = 34.8 ppm, J(31P-195Pt) = 3949 Hz, Table 2]
factory and the 31P{1H} NMR showed single resonances which indicates the presence of Cl– trans to P. The IR spec-
(CDCl3) at δP = 24.4 and 60.5 ppm for the oxide and sulf- trum has νNH at 3054 cm–1, νC=C and νPN at 1642 and
ide, respectively. The selenium analogue exhibited a single 1000 cm–1, respectively, and two νPtCl bands at 305 and
31P{1H} NMR resonance (CDCl3) at δP = 58.1 ppm with 288 cm–1 which support the cis geometry.
selenium satellites [1J(31P-77Se) = 756 Hz] which is typical
The crystal structure of 6 (Table 3, Figure 2) shows that
the molecule is square-planar at Pt. The P(21)–Pt(1)–P(1)
for a P=Se group.[6]
The crystal structure of 4 (Figure 1, Table 1). shows that [98.81(4)°] and Cl(1)–Pt(1)–Cl(2) [84.53(4)°] angles are sig-
in the solid state the molecule forms hydrogen-bonded di- nificantly distorted from the ideal 90° due to the bulky
mers. The NH proton of one molecule is hydrogen-bonded phosphane groups. The Pt–P bond lengths are in the nor-
to the selenium atom of a second and the selenium atom of mal range. In the solid state the X-ray structure displays
the second interacts with the NH proton of the first, leading two intramolecular N–H···Cl hydrogen bonds that result in
to a head to tail type arrangement of the molecules [H(2) two five-membered rings [N(13)–H(13)···Cl(1) 2.34(4) Å
···Se(1A) 2.63, N(2)···Se(1A) 3.61 Å, N(2)–H(2)···Se(1A) N(13)–H(13)···Cl(1) 127(4)°, N(33)–H(33)···Cl(2) 2.34(4) Å,
angle of 174°].
N(33)–H(33)···Cl(2) angle of 128(4)°].
[PdCl2{Ph2PNH(C3H5)}2] (7) was prepared in a similar
way to 6. The expected fragmentation pattern and parent
ion was observed in the FAB mass spectrum whilst the
31P{1H} NMR spectrum showed two peaks at δ = 58.8 and
46.2 ppm which is indicative of a mixture of cis and trans
isomers. The IR bands observed at 3054, 1643 and 997 cm–1
represent νNH, νC=C and νPN, respectively [Equation (2)].
Figure 1. The X-ray structure of Ph2P(Se)NH(C3H5) (4) showing
hydrogen bonding
(2)
Table 1. Selected bond lengths [Å] and angles [o] for Ph2P(Se)-
NH(C3H5) (4)
Reaction of of [{PtCl(µ-Cl)(PEt3)}2] with
1 gave
[Pt(PEt3)Cl2{Ph2PNH(C3H5)}] (8) in a yield of 59 %; δPA
=
1
1
34.2 ppm, δPX = 7.3 ppm, J(31PA-195Pt) = 3979, J(31PX-
4
2
195Pt) = 3479, J(31PA-31PX) = 19 Hz, which is typical for
P(1)–N(2)
1.657(4)
complexes of this type. The PMe2Ph analogue 9 was ob-
tained in a similar fashion. The molecular structures of 8
and 9 (Table 4, Figure 3) confirm that the complexes con-
tain one ligand bound to the platinum atom through the
phosphorus atom; the hydrogen bonding motif is observed
[in 8: N(2)–H(2)···Cl(2) 2.74(4) Å, N(2)–H(2)···Cl(2) angle
of 110(3)°].
[PdCl(C10H8N){Ph2PNH(C3H5)}] (10) was prepared
from 1 and [{PdCl(C10H8N)}2] (C10H8N = metallated
naphthylamine ligand) whilst [RuCl(µ-Cl)(η6-p-MeC6H4-
Se(1)–P(1)
P(1)–C(11)
P(1)–C(17)
N(2)–P(1)–C(11)
N(2)–P(1)–C(17)
C(11)–P(1)–C(17)
C(11)–P(1)–Se(1)
C(17)–P(1)–Se(1)
N(2)–P(1)–Se(1)
P(1)–N(2)–H(2)
2.1082(12)
1.806(4)
1.814(4)
103.30(19)
103.49(18)
105.86(18)
113.32(13)
112.20(14)
117.48(15)
116(3)
Coordination of 1 as a monodentate ligand was estab- iPr){Ph2PNH(C3H5)}] (11) was prepared from [{RuCl(µ-
lished in a number of cases. Thus, reaction of [AuCl(tht)] Cl)(η6-p-MeC6H4 iPr)}2] and 1 (85 % yield). The X-ray
with 1 gave the expected product [AuCl{Ph2PNH(C3H5)}] structure of 11 (Table 5, Figure 4) confirms that the com-
(5) [Table 2 summarises spectroscopic data], and reaction of plex contains one ligand and is bound to the ruthenium
714
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Eur. J. Inorg. Chem. 2005, 713–720

Preparation and Coordination Chemistry of n-Allylaminophosphane
FULL PAPER
Table 2. Characterisation data for Ph2PNH(C3H5) and its derivatives
Compound
31P{1H}
NMR
IR [cm–1
]
Microanalysis: found (calcd.)
δp [ppm]
νPN
νNH
νC=C
νP=E
νMCl
C
H
N
Ph2PNH(C3H5) (1)
42.5
–
–
72.27
7.37
5.58
(74.67)
69.74
(70.03)
66.01
(65.91)
55.97
(56.07)
37.98
(38.03)
48.23
(48.14)
54.80
(54.61)
40.61
(40.38)
42.99
(42.85)
56.93
(57.16)
55.71
(54.85)
54.32
(54.56)
47.07
(46.95)
43.95
(43.04)
36.53
(35.52)
52.06
(6.68)
6.22
(6.27)
6.09
(5.90)
5.25
(5.02)
2.76
(3.40)
4.10
(4.31)
4.67
(4.89)
4.38
(5.01)
2.26
(4.22)
3.93
(4.60)
5.62
(5.52)
5.78
(5.68)
4.85
(4.89)
4.26
(3.85)
2.99
(3.18)
4.60
(5.81)
5.15
(5.44)
5.11
(5.12)
4.43
(4.36)
3.07
(2.96)
3.65
(3.74)
4.06
(4.25)
2.49
(2.24)
2.08
(2.17)
5.24
(5.33)
2.71
(2.56)
2.44
(2.55)
2.13
(2.19)
2.70
(3.35)
2.60
(2.76)
3.70
Ph2P(O)NH(C3H5) (2)
24.4
993
997
991
996
1000
997
1002
3189
3170
3177
3069
3054
3054
3072
3053
3049
3051
3063
3058
3054
3055
3069
1641
1642
1644
1643
1642
1643
1641
1642
1639
1642
1642
1640
–
1181
–
Ph2P(S)NH(C3H5) (3)
60.5
689
573
–
–
Ph2P(Se)NH(C3H5) (4)
58.1[a]
64.9
–
[AuCl{Ph2PNH(C3H5)}] (5)
[PtCl2{Ph2PNH(C3H5)}2] (6)
[PdCl2{Ph2PNH(C3H5)}2] (7)
[Pt(PEt3Cl2{Ph2PNH(C3H5)}] (8)
[Pt(PMe2Ph)Cl2{Ph2PNH(C3H5)}] (9)
[PdCl(C10H8N){Ph2PNH(C3H5)}] (10)
323
34.8[b]
58.8, 46.2
34.2, 7.3[f]
–
305,
288
297,
277
309,
283
313,
283
289
–
–
35.3, –14.2[g] 1000
–
65.0
61.3
993
996
995
994
996
998
997
–
[Ru Cl(µ-Cl)(η6-p-MeC6H4 iPr)
{(Ph2PNH(C3H5)}] (11)
–
290,
283
279,
267
291,
280
318,
281
328,
289
–
[RhCl(µ-Cl)(η5-C5Me5){(Ph2PNH(C3H5)}] (12) 66.4[e]
–
[IrCl(µ-Cl)(η5-C5Me5){(Ph2PNH(C3H5)}] (13) 34.5
–
[PdCl2{Ph2PNH(C3H5)}] (14)
[PtCl2{Ph2PNH(C3H5)}] (15)
[Pt{Ph2PNH(C4H8O)}2] (16)
93.6
–
63.5[c]
91.4[d]
3051
–
–
–
(51.96)
(5.18)
(3.79)
[a] 1J{31P-77Se} = 756 Hz. [b] 1J{31P-195Pt} = 3949 Hz. [c] 1J{31P-195Pt} = 3481 Hz. [d] 1J{31P-195Pt} = 2294 Hz. [e] 1J{31P-103Rh} = 148 Hz.
[f] 1J{31PA-195Pt} = 3979, 1J{31PX-195Pt} = 3479, 2J(31PA-31PX) = 19 Hz. [g] 1J{31PA-195Pt}= 3878, 1J{31PX-195Pt} = 3625, 2J(31PA-31PX)
19 Hz.
Table 3. Selected bond lengths [Å] and angles [o] for
[PtCl2{Ph2PNH(C3H5)}2] (6)
6
Pt(1)–Cl(1)
Pt(1)–Cl(2)
Pt(1)–P(1)
Pt(1)–P(21)
P(1)–N(13)
P(21)–N(33)
N(13)–C(14)
N(33)–C(34)
2.3644(10)
2.3649(12)
2.2625(10)
2.251(9)
1.663(3)
1.660(4)
1.457(5)
1.463(6)
3.039(3)
3.050(4)
88.22(4)
84.53(4)
108.03(12)
98.81(4)
172.97(3)
88.45(4)
172.59(4)
125.3(3)
109.64(13)
123.0(3)
N(13)···Cl(1)
N(33)···Cl(2)
P(1)–Pt(1)–Cl(1)
Cl(1)–Pt(1)–Cl(2)
N(13)–P(1)–M(1)
P(21)–Pt(1)–P(1)
P(21)–Pt(1)–Cl(1)
P(21)–Pt(1)–Cl(2)
P(1)–Pt(1)–Cl(2)
C(14)–N(13)–P(1)
N(33)–P(21)–Pt(1)
C(34)–N(33)–P(21)
Figure 2. The X-ray structure of [PtCl2{Ph2PNH(C3H5)}2] (6)
atom through the phosphorus atom with a P(1)–Ru(1) bond
length of 2.3404(11) Å and similar intramolecular hydrogen
bonding to 8.
Eur. J. Inorg. Chem. 2005, 713–720
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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A. M. Z Slawin, J. Wheatley, J. D. Woollins
FULL PAPER
Table 4. Selected bond lengths [Å] and angles [o] for [Pt(PEt)3-
Table 5. Selected bond lengths [Å] and angles [o] for [RuCl(µ-
Cl2{Ph2PNH(C3H5)}] (8) and [Pt(PPhMe2)Cl2{Ph2PNH(C3H5)}] Cl)(η6-p-MeC6H4 iPr){Ph2PNH(C3H5)}] (11)
(9)
11
8
9
Ru(1)–Cl(1)
Ru(1)–Cl(2)
Ru(1)–P(1)
P(1)–N(2)
2.4314(11)
2.4037(12)
2.3404(11)
1.657(3)
Pt(1)–Cl(1)
Pt(1)–Cl(2)
Pt(1)–P(1)
Pt(1)–P(2)
P(1)–N(2)
P(1)–C(11)
P(1)–C(17)
P(1)–Pt(1)–P(2)
Cl(2)–Pt(1)–Cl(1)
N(2)–P(1)–C(11)
N(2)–P(1)–C(17)
C(11)–P(1)–C(17)
N(2)–P(1)–Pt(1)
C(11)–P(1)–Pt(1)
C(17)–P(1)–Pt(1)
2.3496(19)
2.3716(17)
2.2587(18)
2.2520(18)
1.658(6)
1.822(6)
1.820(7)
96.82(6)
85.09(6)
110.6(3)
100.9(3)
105.8(3)
106.4(2)
111.9(2)
120.5(2)
2.3481(17)
2.3741(16)
2.2505(17)
2.2487(16)
1.677(5)
1.824(6)
1.820(6)
96.14(6)
86.45(6)
109.1(3)
100.3(3)
105.8(3)
108.4(2)
110.9(2)
121.5(2)
P(1)–C(11)
P(1)–C(17)
1.823(4)
1.827(4)
N(2)···Cl(2)
3.202(3)
88.54(4)
85.35(4)
87.06(4)
105.94(18)
106.69(17)
104.36(18)
112.64(12)
111.88(12)
114.61(13)
P(1)–Ru(1)–Cl(1)
P(1)–Ru(1)–Cl(2)
Cl(2)–Ru(1)–Cl(1)
N(2)–P(1)–C(11)
N(2)–P(1)–C(17)
C(11)–P(1)–C(17)
N(2)–P(1)–Ru(1)
C(11)–P(1)–Ru(1)
C(17)–P(1)–Ru(1)
Figure 4. The X-ray structure of [RuCl(µ-Cl)(η6-p-MeC6H4 iPr)
{Ph2PNH(C3H5)}] (11) showing hydrogen bonding
Figure 3. The X-ray structure of [Pt(PEt)3Cl2{Ph2PNH(C3H5)}]
(8), the structure of [Pt(PPhMe2)Cl2{Ph2PNH(C3H5)}] (9) is very
similar and is not illustrated
Table 2]. The magnitude of the Pt-P coupling constants
strongly indicates the coordination of both phosphane and
alkene group.
The reaction of Ph2PNH(C3H5) with [{RhCl(µ-Cl)(η5-
C5Me5)}2] and [{IrCl(µ-Cl)(η5-C5Me5)}2] proceeded in sim-
ilar fashion to give [RhCl(µ-Cl)(η5-C5Me5){Ph2PNH-
(C3H5)}] (12) and [IrCl(µ-Cl)(η5-C5Me5){Ph2PNH(C3H5)}]
(13) in good yields [67 % and 65 % respectively, Equation
(3), Table 2].
(4)
In an interesting transformation, [Pt{Ph2PNH(C3H8O)}2]
(16), was obtained by reaction of KOtBu in methanol
with 6 (51 % yield). The reaction probably proceeds by nu-
cleophillic attack of methoxide though we have not ob-
served this reaction for other complexes. The 31P{1H}
(3)
NMR spectrum showed a single peak at δP = 91.4 ppm with
1
In order to obtain a bidentate complex we treated 1 with platinum satellites at J(31P-195Pt) = 2294 Hz. The IR spec-
1 equiv. of [MCl2(cod)] to give 14 and 15 [Equation (4), trum shows absorptions at 2873–2809 cm–1, which corre-
716
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2005, 713–720

Preparation and Coordination Chemistry of n-Allylaminophosphane
FULL PAPER
phenone and distillation under nitrogen. Dichloromethane was
heated to reflux in the presence of calcium hydride and distilled
under nitrogen. Toluene and hexane were heated to reflux in the
presence of sodium and distilled under nitrogen. The complexes
[PtMeX(cod)] (X = Cl or Me),[8] [{Pd(µ-Cl)(η3-C3H5)}2],[9] [Cu-
spond to νOMe vibrations along with vibrations at 3069 and
997, which are assigned to νNH and νPN, respectively. The
FAB mass spectral analysis gave the appropriate parent ion
and fragmentation pattern and the microanalysis shows
good results for the suggested structure. The crystal struc-
ture of 16 (Table 6, Figure 5) shows that in the solid state
the molecule occurs as hydrogen-bonded dimers. [H(1N)
···O(5) 2.241(19) Å, N(1)···O(5) 3.164(4) Å, N(1)–H(1N)
···O(5) angle of 157(4)°].
(MeCN)4][PF6],[10] [AuCl(tht)] (tht
=
tetrahydrothiophene),[11]
[MCl2(cod)] (M = Pt or Pd),[12,13] [{RuCl(µ-Cl)(η6-p-MeC6H4-
iPr)2}],[14] [{Rh(µ-Cl)(cod)}2],[15] [{MCl(µ-Cl)(η5-C5Me5)}2] (M =
Rh or Ir),[16] [{PtCl(µ-Cl)(PMe2Ph)}2],[17] [{PtCl(µ-Cl)(PMe2-
Ph)}2][18] and [{Pd(µ-Cl)(C10H8N)}2][19] were prepared according to
literature procedures. Chlorodiphenylphosphane and allylamine
were distilled prior to use. Et3N (99 % purity), tBuOK (95 % pu-
rity), H2O2 (30 wt.% in H2O) and reagent grade KBr were used
without further purification. IR spectra were recorded as KBr discs
in the range 4000–200 cm–1 with a Perkin–Elmer 2000 FTIR/
RAMAN spectrometer. NMR spectra were recorded with a Gem-
ini 2000 spectrometer (operating at 121.4 MHz for 31P and
Table 6. Selected bond lengths [Å] and angles [°] for
[Pt{Ph2PNH(C3H5OMe)2}] (16)
16
Pt(1)–C(3)
Pt(1)–P(1)
P(1)–N(1)
2.113(4)
2.2743(9)
1.664(3)
1
300 MHz for H). Microanalyses were performed by the St. And-
P(1)–C(7)
1.832(4)
rews University service and mass spectra by the Swansea Mass
Spectrometer Service.
P(1)–C(13)
N(1)–C(2)
1.827(4)
1.451(5)
C(3)–Pt(1)–P(1)
N(1)–P(1)–C(13)
N(1)–P(1)–C(7)
C(13)–P(1)–C(7)
N(1)–P(1)–Pt(1)
C(13)–P(1)–Pt(1)
C(7)–P(1)–Pt(1)
C(2)–N(1)–P(1)
81.56(11)
105.68(18)
106.47(18)
102.15(17)
104.19(12)
119.72(11)
117.51(12)
117.6(3)
Ph2PNH(C3H5) (1): Allylamine (3.671 g, 64.3 mmol) and triethyl-
amine (6.831 g, 67.5 mmol) were added together in dry THF
(50 mL). Chlorodiphenylphosphane (14.894 g, 67.5 mmol) in dry
THF (50 mL) was added dropwise with stirring overnight. Triethyl-
amine hydrochloride was removed by filtration under nitrogen and
the solvent removed in vacuo to yield a colourless oil which was
purified by distillation (132 °C/0.2 Torr) and storing under nitrogen
in the freezer which yielded a colourless waxy solid. Yield 6.283 g,
41 %. C15H16NP (241.3): calcd. C 74.67, H 6.68, N 5.81; found C
1
74.27, H 7.37, N 5.58. 31P{1H} NMR (CDCl3): δ = 42.5 ppm. H
NMR (CDCl3): δ = 7.3 (m, 10 H, aromatic), 5.8 (m, 1 H, CH), 5.2
(m, 1 H, CH2), 5.1 (m, 1 H, CH2), 3.5 (m, 2 H, NCH2) and 1.9 (s,
1 H, NH) ppm. EI+ MS: m/z = 242 [M + 1]+.
Ph2P(O)NH(C3H5) (2): Ph2PNH(C3H5) (461 mg, 1.9 mmol) was
dissolved in dichloromethane (10 mL). Urea/hydrogen peroxide
(180 mg, 1.9 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 mL), dried with mag-
nesium sulfate and the solvents were evaporated to dryness to yield
a colourless solid. Yield 338 mg, 67 %. C15H16NOP (257.3): calcd.
C 70.03, H 6.27, N 5.44; found C 69. 74, H 6.22, N 5.15. 31P{1H}
1
NMR (CDCl3): δ = 24.4 ppm. H (CDCl3): δ = 7.3 (m, 10 H, aro-
matic), 5.9 (m, 1 H, CH), 5.3 (m, 1 H, CH2), 5.1 (m, 1 H, CH2),
3.5 (m, 2 H, NCH2) and 2.9 (br.s, 1 H, NH) ppm. EI+ MS: m/z =
257 [M]. IR (KBr disc): ν = 3189, 1641, 1181, 993 cm–1.
˜
Ph2P(S)NH(C3H5) (3): Ph2PNH(C3H5) (420 mg, 1.7 mmol) and el-
emental sulfur (56 mg, 1.7 mmol) were dissolved in dry toluene
(10 mL) to yield a yellow solution which was stirred overnight. The
solvent was reduced to 1 mL before addition of hexane (10 mL) to
precipitate a colourless solid that was isolated by filtration. Yield
246 mg, 52 %. C15H16NPS (273.3): calcd. C 65.91, H 5.90, N 5.12;
found C 66.01, H 6.09, N 5.11. 31P{1H} NMR (CDCl3): δ =
Figure 5. The X-ray structure of [Pt{Ph2PNH(C3H5OMe)2}] (16)
showing hydrogen bonding
This paper clearly demonstrates the ability of (al-
lylamino)phosphane to behave as a monodenate and biden-
tate ligand and illustrates a potentially useful nucleophilic
addition at the allyl group.
1
60.5 ppm. H NMR (CDCl3): δ = 7.3 (m, 10 H, aromatic), 5.9 (m,
1 H, CH), 5.2 (m, 1 H, CH2), 5.1 (m, 1 H, CH2), 3.5 (m, 2 H,
NCH2) and 2.4 (br. s, 1 H, NH) ppm. EI+ MS: m/z = 273 [M]. IR
(KBr disc): ν = 3170, 1642, 997, 689 cm–1.
˜
Ph2P(Se)NH(C3H5) (4): Ph2PNH(C3H5) (235 mg, 1.0 mmol) and
grey selenium (77 mg, 1.0 mmol) were refluxed in dry toluene
(10 mL) 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 mL to yield a colourless solid that was isolated
by suction filtration and dried in vacuo. Yield 269 mg, 86 %.
Experimental Section
General: General conditions were as described previously.[7] Unless
otherwise stated, all reactions were carried out under oxygen-free
nitrogen using standard Schlenk techniques. Diethyl ether and
THF were purified by reflux in the presence of sodium/benzo-
Eur. J. Inorg. Chem. 2005, 713–720
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
717

A. M. Z Slawin, J. Wheatley, J. D. Woollins
FULL PAPER
C15H16NPSe (320.2): calcd. C 56.07, H 5.02, N 4.36; found C 55.97, of diethyl ether (20 mL) to precipitate a colourless solid that was
H 5.25, N 4.43. 31P{1H} NMR (CDCl3): δ = 58.1 ppm [1J(31P-77Se) isolated by suction filtration and dried in vacuo. Yield 55 mg, 62 %.
= 756 Hz]. 1H NMR (CDCl3): δ = 7.3 (m, 10 H, aromatic), 5.9 (m,
1 H, CH), 5.3 (q, 1 H, CH2), 5.1 (m, 1 H, CH2), 3.5 (m, 2 H,
NCH2) and 2.3 (br. s, 1 H, NH) ppm. EI+ MS: m/z = 322 [M]. IR
C23H27Cl2NP2Pt (645.4): calcd. C 42.85, H 4.22, N 2.17; found C
42., H 2.26, N 2.08. 31P{1H} NMR (CDCl3): δ(PA) = 35.3 (d) ppm
[1J(31PA-195Pt) = 3878 Hz]; δ(PX) = –14.2 (d) ppm [1J(31PX-195Pt) =
2
1
(KBr disc): ν = 3177, 1644, 991, 573 cm–1.
3625 Hz. J(31PA-31PX) 19 Hz]. H NMR (CDCl3): δ = 7.4 (m, 15
H, aromatic), 5.6 (m, 1 H, CH), 5.1 (m, 1 H, CH2), 4.9 (m, 1 H,
CH2), 4.5 (br.s, 1 H, NH), 3.1 (m, 2 H, NCH2) and 1.7 [d, 6 H,
˜
[AuCl{Ph2PNH(C3H5)}] (5): Ph2PNH(C3H5) (78 mg, 0.3 mmol)
and [AuCl(tht)] (103 mg, 0.3 mmol) were dissolved in CH2Cl2
(5 mL) and the mixture stirred overnight in the dark. Hexane
(20 mL) was added to precipitate a colourless solid that was iso-
lated by suction filtration. Yield 44 mg, 29 %. C15H16AuClPN
(473.7): calcd. C 38.03, H 3.40, N 2.96; found C 37.98, H 2.76, N
2
3J(195Pt-1H) = 32 Hz, J(31P-1H) = 11 Hz, PMe] ppm. ES+ MS: m/
z 645 = [M + H]+, 610 [M – Cl]+, 575 [M – 2 Cl]2+. IR (KBr disc):
ν= 3053, 1642, 1000, 313, 283 cm–1.
˜
[PdCl(C10H8N){Ph2PNH(C3H5)}] (10): To a CH2Cl2 (10 mL) sus-
pension of [{PdCl(C10H8N)}2] (61 mg, 0.1 mmol) was added drop-
wise a CH2Cl2 solution of Ph2PNH(C3H5) (52 mg, 0.2 mmol) over
10 minutes to yield a colourless solution. After stirring for a further
30 minutes the solution was filtered through a Celite plug to remove
any insoluble material remaining before reducing the solvent vol-
ume to 1 mL and addition of diethyl ether (20 mL) to precipitate
a tan coloured microcrystalline solid that was isolated by filtration.
Yield 78 mg, 69 %. C25H24ClN2PPd (525.3): calcd. C 57.16, H 4.60,
N 5.33; found C 56.93, H 3.93, N 5.24. 31P{1H} NMR (CDCl3): δ
1
3.07. 31P{1H} NMR (CDCl3): δ = 64.9 ppm. H NMR (CDCl3): δ
= 7.4 (m, 10 H, aromatic), 5.9 (m, 1 H, CH), 5.2 (m, 1 H, CH2),
5.1 (m, 1 H, CH2), 3.6 (m, 2 H, NCH2), 2.5 (br.s, 1 H, NH) ppm.
FAB+ MS: m/z = 496 [M + Na]+, 473 [M]+, 438 [M – Cl]+. IR
(KBr disc): ν= 3069, 1643, 996, 323 cm–1.
˜
[PtCl2{Ph2PNH(C3H5)}2] (6): Ph2PNH(C3H5) (161 mg, 0.7 mmol)
and [PtCl2(cod)] (125 mg, 0.3 mmol) were dissolved in dry CH2Cl2
(10 mL) to yield a colourless solution which was stirred overnight
before reducing the solvent volume to 0.5 mL and addition of di-
ethyl ether (20 mL) to precipitate a colourless solid which was iso-
lated by suction filtration and dried in vacuo. Yield 226 mg, 90 %.
C30H32P2N2PtCl2 (748.5): calcd. C 48.14, H 4.31, N 3.74; found C
48.23, H 4.10, N 3.65. 31P{1H} NMR (CDCl3): δ = 34.8 ppm
1
= 65.0 ppm. H NMR (CDCl3): δ = 9.6–7.8 (m, 6 H, naphthalene
aromatic), 7.3 (m, 10 H, aromatic), 5.7 (m, 1 H, CH), 5.2 (m, 1 H,
CH2), 5.0 (m, 1 H, CH2), 4.5 (br.s, 1 H, NH), 3.4 (m, 2 H, NCH2),
2
2.8 [d, J(31P-1H) 5 Hz, 2 H, CH2] ppm. ES+ MS: m/z = 489 [M –
1
Cl]+. IR (KBr disc): ν= 3049, 1639, 993, 28 cm–1.
[1J(31P-195Pt) 3949 Hz]. H NMR (CDCl3): δ = 7.4 (m, 20 H, aro-
˜
[RuCl(µ-Cl)(η6-p-MeC6H4 iPr){Ph2PNH(C3H5)}] (11): Ph2PNH-
(C3H5) (170 mg, 0.7 mmol) and [{RuCl(µ-Cl)(η6-p-MeC6H4 iPr)}2]
(54 mg, 0.1 mmol) were dissolved in CH2Cl2 (5 mL) to yield a dark
red solution that was stirred for 30 min. The solvent was reduced to
0.5 mL before addition of hexane (10 mL to precipitate an orange
microcrystalline solid that was isolated by suction filtration and
dried in vacuo. Yield 82 mg, 85 %. C25H30Cl2NPRu (547.5): calcd.
C 54.85, H 5.52, N 2.56; found C 55.71 54.85, H 5.62, N 2.71.
matic), 5.5 (m, 2 H, CH), 5.0 (m, 2 H, CH2), 4.9 (m, 2 H, CH2),
4.1 (br.s, 2 H, NH) and 3.5 (m, 4 H, NCH2) ppm. FAB+ MS: m/z
= 713 [M – Cl]+, 677 [M – 2 Cl]2+. IR (KBr disc): ν= 3054, 1642,
˜
1000, 305, 288 cm–1.
[PdCl2{Ph2PNH(C3H5)}2] (7): Ph2PNH(C3H5) (179 mg, 0.7 mmol)
and [PdCl2(cod)] (106 mg, 0.4 mmol) were dissolved in CH2Cl2
(10 mL) and stirred overnight. The solvent volume was reduced to
0.5 mL before addition of hexane (20 mL) to precipitate a yellow
solid that was isolated by filtration and dried in vacuo. Yield
224 mg, 91 %. C30H32Cl2N2P2Pd (659.9): calcd. C 54.61, H 4.89, N
4.25; found C 54.80, H 4.67, N 4.06. 31P{1H} NMR (CDCl3): δ =
1
31P{1H} NMR (CDCl3): δ = 61.3 ppm. H NMR: δ = 7.3 (m, 14
H, aromatic), 5.5 (m, 1 H, CH), 5.2 (m, 1 H, CH2), 5.1 (m, 1 H,
CH2), 3.5 (m, 2 H, NCH2), 2.9 (br. s, 1 H, NH), 2.6 (m, 1 H, CH),
1.2 (m, 3 H, CH3), 0.8 (m, 6 H, CH3) ppm. FAB+ MS: m/z = 570
[M + Na]+, 547 [M]+, 512 [M – Cl]+, 476 [M – 2 Cl]2+. IR (KBr
1
58.8 and 46.2 ppm, cis and trans isomers. H NMR (CDCl3): δ =
7.5–7.2 (m, 20 H, aromatic), 5.6 (m, 2 H, CH), 5.2 (m, 2 H, CH2),
5.1 (m, 2 H, CH2), 3.5 (m, 4 H, NCH2) and 4.1 (br.s, 2 H, NH)
ppm. FAB+ MS: m/z = 624 [M – Cl]+, 588 [M – 2 Cl]2+. IR (KBr
disc): ν = 3051, 1642, 996, 290, 283 cm–1.
˜
[RhCl(µ-Cl)(η5-C5Me5){Ph2PNH(C3H5)}] (12): Ph2PNH(C3H5)
(45 mg, 0.2 mmol) and [{RhCl(µ-Cl)(η5-C5Me5)}2] (58 mg,
0.1 mmol) were dissolved in CH2Cl2 (10 mL) to yield a blood red
solution that stirred for 30 min before reducing the solvent to 1 mL
and addition of diethyl ether (20 mL) to precipitate a red micro-
crystalline solid that was isolated by suction filtration and dried in
vacuo. Yield 69 mg, 67 %. C25H31Cl2NPRh (550.3): calcd. C 54.56,
H 5.68, N 2.55; found C 54.32 , H 5.78, N 2.44. 31P{1H} NMR
(CDCl3): δ = 66.4 ppm [1J(31P-103Rh) = 148 Hz]. 1H NMR
(CDCl3): δ = 7.3 (m, 10 H, aromatic), 5.6 (m, 1 H, CH), 5.2 (m, 1
H, CH2), 5.1 (m, 1 H, CH2), 3.3 (m, 2 H, NCH2), 3.2 (br. s, 1 H,
NH), 1.3 (s, 15 H, CH3) ppm. FAB+ MS: m/z = 572 [M + Na]+,
disc): ν= 3054, 1643, 997, 297, 277 cm–1.
˜
[Pt(PEt3)Cl2{Ph2PNH(C3H5)}] (8): To a CH2Cl2 (10 mL) solution
of [{PtCl(µ-Cl)(PEt3)}2] (56 mg, 0.07 mmol) was added dropwise a
CH2Cl2 (10 mL) solution of Ph2PNH(C3H5) (35 mg, 0.1 mmol)
with stirring to yield a pale yellow solution. After 30 minutes the
solvent was reduced to 1 mL before addition of diethyl ether
(20 mL) to precipitate a colourless solid that was isolated by suc-
tion filtration. Yield 54 mg, 59 %. C21H31Cl2NP2Pt (625.4): calcd.
C 40.38, H 5.01, N 2.24; found C 40.61, H 4.38, N 2.49. 31P{1H}
NMR (CDCl3): δ(PA) = 34.2 (d) ppm [1J(31PA-195Pt) = 3979 Hz];
δ(PX) = 7.3 (d) ppm [1J(31PX-195Pt) = 3479 Hz, 2J(31PA-31PX)
514 [M – Cl]+, 474 [M – 2 Cl]2+. IR (KBr disc): ν = 3063, 1642,
1
˜
=19 Hz]. H NMR (CDCl3): δ = 7.3 (m, 10 H, aromatic), 5.7 (m,
995, 279, 267 cm–1.
1 H, CH), 5.2 (m, 1 H, CH2), 5.0 (m, 1 H, CH2), 3.5 (m, 2 H,
NCH2), 3.2 (br.s, 1 H, NH), 1.5 (m, 6 H, PCH2) and 0.9 (m, 9 H,
[IrCl(µ-Cl)(η5-C5Me5){Ph2PNH(C3H5)}] (13): Ph2PNH(C3H5)
(42 mg, 0.2 mmol) and [{IrCl(µ-Cl)(η5-C5Me5)}2] (69 mg,
0.1 mmol) were dissolved in CH2Cl2 (10 mL) to yield an orange
Me) ppm. ES+ MS: m/z = 590 [M – Cl]+. IR (KBr disc): ν= 3072,
˜
1641, 1002, 309, 283 cm–1.
[Pt(PMe2Ph)Cl2{Ph2PNH(C3H5)}] (9): Ph2PNH(C3H5) (33 mg, solution. The solvent was reduced to 1 mL before diethyl ether was
0.1 mmol) in CH2Cl2 (10 mL) was added dropwise to a CH2Cl2 added to precipitate a yellow microcrystalline solid that was iso-
(10 mL) solution of [{PtCl(µ-Cl)(PMe2Ph)}2] 56 mg, 0.07 mmol)
over 10 minutes with stirring. The solution was stirred for a further
30 minutes before reduction of the solvent to 1 mL and addition
lated by filtration and dried in vacuo. Yield 72 mg, 65 %.
C25H31Cl2IrNP (639.6): calcd. C 46.95, H 4.89, N 2.19; found C
1
47.07, H 4.85, N 2.13. 31P{1H} NMR (CDCl3): δ = 34.5 ppm. H
718
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 713–720

Preparation and Coordination Chemistry of n-Allylaminophosphane
FULL PAPER
Table 7. Crystal data for Ph2PNH(C3H5) and derivatives
Compound
4
6
8
9
11
16
Empirical formula
M
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C17H16N3PSe
320.22
monoclinic
P21/n
12.246(3)
9.317(2)
12.711(3)
90
C30H32Cl2N2P2Pt
748.51
monoclinic
P21/n
10.012(3)
15.065(4)
19.717(6)
90
91.56(10)
90
C21H31Cl2NP2Pt
625.40
triclinic
C23H27Cl2NP2Pt
649.39
triclinic
C25H30Cl2NPRu
547.44
monoclinic
P21/n
9.918(3)
13.782(4)
17.566(5)
90
94.880(5)
90
C32H38N2O2P2Pt
739.67
monoclinic
C2/c
20229(3)
10.8193(17)
16.926(3)
90
123.002(2)
90
¯
P1
¯
P1
8.835(2)
9.741(2)
14.634(3)
87.302(4)
87.343(4)
71.362(3)
2
9.2943(12)
9.7402(13)
14.1561(19)
90.661(2)
94.862(2)
112.151(2)
2
β [°]
γ [°]
Z
92.261(5)
90
4
4
4
4
µ [mm–1
]
2.684
5.029
6.254
6.311
0.958
4.650
Reflections measured
5982
12495
5879
5970
10269
8848
Independent reflections
2066
4181
3327
3353
3421
2765
Final R1, wR2 [I Ͼ 2σ(I)] 0.0381, 0.0917
0.0214, 0.0515
0.0361, 0.0967
0.0317, 0.0788
0.0343, 0.0783
0.0229, 0.0473
NMR (CDCl3): δ = 7.3 (m, 10 H, aromatic), 5.6 (m, 1 H, CH), 5.2 MeO) ppm. FAB+ MS: m/z = 740 [M]+. IR (KBr disc): ν = 3069,
˜
(m, 1 H, CH2), 5.1 (m, 1 H, CH2), 3.5 (m, 2 H, NCH2), 3.2 (br. s, 3045, 2873–2809 (m), 997 cm–1.
1 H, NH), 1.3 (s, 15 H, CH3) ppm. FAB+ MS: m/z = 604 [M –
X-ray Crystallography: X-ray diffraction studies were performed
Cl]+, 568 [M – 2 Cl]2+. IR (KBr disc): ν = 3058, 1640, 994, 291,
˜
using a Bruker SMART diffractometer with graphite-monochro-
280 cm–1.
mated Mo-K radiation. The structures were solved by direct
α
[PdCl2{Ph2PNH(C3H5)}] (14): Ph2PNH(C3H5) (52 mg, 0.2 mmol) methods, non-hydrogen atoms were refined with anisotropic dis-
in CH2Cl2 (5 mL) was added dropwise to CH2Cl2 (5 mL) solution
of [PdCl2(cod)] (53 mg, 0.2 mmol). After stirring for 30 min, the
solvent was reduced in vacuo to 0.5 mL before precipitating a yel-
low microcrystalline solid upon addition of hexane (10 mL) and
isolation by suction filtration. Yield 65 mg, 83 %. C15H16PNPdCl2
placement parameters; hydrogen atoms bound to carbon atoms
were idealised, the NH protons were located by a ∆F map. Struc-
tural refinements were made by the full-matrix least-squares
2
method on F using SHELXTL.[20] Details are given in Table 7.
Full lists of structure refinement data, atomic coordinates, bond
lengths and angles, anisotropic displacement parameters and hy-
(418.6): calcd. C 43.04, H 3.85, N 3.35; found C 43.95, H 4.26, N
1
2.70. 31P{1H} NMR (CD2Cl2): δ = 93.6 ppm. H NMR (CD2Cl2): drogen atom parameters have been deposited as supplementary
δ = 7.35 (m, 10 H, aromatic), 5.6 (m, 1 H, CH), 5.2 (m, 1 H, CH2),
material, CCDC-239884 to –239889 contain the supplementary
5.1 (m, 1 H, CH2), 3.5 (m, 2 H, NCH2) and 4.1 (br. s, 1 H, NH) crystallographic data for this paper. These data can be obtained
ppm. FAB+ MS: m/z = 382 [M – Cl]+, 347 [M – 2 Cl]2+. IR (KBr
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
disc): ν = 3054, 996, 318, 281 cm–1.
˜
[PtCl2{Ph2PNH(C3H5)}] (15): Ph2PNH(C3H5) (43 mg, 0.2 mmol)
in CH2Cl2 (5 mL) was added dropwise to a CH2Cl2 (5 mL) solution
of [PtCl2(cod)] (58 mg, 0.2 mmol) over 2.5 h. The solvent was re-
duced to 1 mL before addition of hexane (10 mL) to yield an off-
white sticky solid on reduction of solvent. The sticky solid was
subsequently dissolved in CH2Cl2 (0.5 mL) before addition of pe-
troleum ether (40–60°C) (10 mL) to yield a colourless solid that was
isolated by suction filtration. Yield 51 mg, 65 %. C15H16Cl2NPPt
(507.2): calcd. C 35.52, H 3.18, N 2.76; found C 36.53, H 2.99, N
2.60. 31P{1H} NMR (CD2Cl2): δ = 63.5 ppm [1J(31P-195Pt) =
3481 Hz]. 1H NMR (CD2Cl2): δ = 7.35 (m, 10 H, aromatic), 5.5
(m, 1 H, CH), 5.2 (m, 1 H, CH2), 5.1 (m, 1 H, CH2), 3.5 (m, 2 H,
NCH2) and 4.1 (br. d, J = 8 Hz, 1 H, NH) ppm. FAB+ MS: m/z =
[1] K. J. Coutinho; R. S. Dickson, G. D. Fallon; W. R. Jackson, T.
De Simone, B. W. Skelton, A. H. White, J. Chem. Soc., Dalton
Trans. 1997, 3193.
[2] B. Cornils, E. Wilbus, Chem. Tech. 1995, 33; B. Cornils, Angew.
Chem. Int. Ed. Engl. 1995, 34, 1575.
[3] E. Billig, A. G. Abatjoghe, D. R. Bryant, US Pat. 4668651,
1987; 4769498, 1988; G. D. Cuny, S. L. Buchwald, J. Am.
Chem. Soc. 1993, 115, 2066; T. Higashizima, N. Sakai, K. No-
zaki, H. Takaya, Tetrahedron Lett. 1994, 35, 2023; M. E. Davis,
Chem. Tech. 1992, 498; W. A. Herrmann, C. W. Kohlpaintner,
Angew. Chem. Int. Ed. Engl. 1993, 32, 1524; S. M. Aucott,
M. L. Clarke, A. M. Z. Slawin, J. D. Woollins, JCS Dalton
2001, 972; S. M. Aucott, A. M. Z. Slawin, J. D. Woollins, J. Or-
ganomet. Chem. 1999, 582, 83; M. L. Clarke, A. M. Z. Slawin,
M. V. Wheatley, J. D. Woollins, J. Chem. Soc., Dalton Trans.
2001, 3421; A. M. Z. Slawin, M. Wainwright, J. D. Woollins,
New J. Chem. 2000, 24, 69; A. M. Z. Slawin, M. Wainwright,
J. D Woollins, J. Chem. Soc., Dalton Trans. 2002, 513.
[4] L. V. Interrante, M. A. Bennet, R. S. Nyholm, Inorg. Chem.
1966, 5, 2212; M. A. Bennett, L. V. Interrante, R. S. Nyholm,
Z. Naturforsch. B: Anorg. Chem. Org. Chem. 1965, 20, 633;
P. R. Brookes, J. Organomet. Chem. 1972, 42, 415.
472 [M – Cl]+, 436 [M – 2 Cl]2+. IR (KBr disc): ν = 3055, 998, 328,
˜
289 cm–1.
[Pt{Ph2PNH(C4H8O)}2] (16): To a CH3OH (10 mL suspension of
[PtCl2{Ph2PNH(C3H5)}2] (100 mg, 0.1 mmol) was added potas-
sium tert-butoxide (30 mg, 0.2 mmol) with stirring to yield a
colourless precipitate after 1 h. This microcrystalline solid was sub-
sequently isolated by suction filtration and dried in vacuo. Yield
46 mg, 51 %. C32H38N2O2P2Pt (739.7): calcd. C 51.96, H 5.18, N
3.79; found C 52.06, H 4.60, N 3.70. 31P{1H} NMR (CDCl3): δ =
91.4 ppm [1J(31P-195Pt) = 2294 Hz]. 1H NMR (CDCl3): δ = 7.4 (m,
20 H, aromatic), 5.9 (m, 2 H, CH), 5.2 (m, 2 H, CH2), 5.1 (m, 2
H, CH2), 3.6 (m, 4 H, NCH2), 2.5 (br. s, 2 H, NH), 1.5 (s, 6 H,
[5] E. Lindner, C. Scheytt, P. Wegner, J. Organomet. Chem. 1986,
308, 311; L. P. Barthel-Rosa, K. Maitra, J. Fischer, J. H. Nel-
son, Organometallics 1997, 16, 1714; H.-L. Ji, J. H. Nelson, A.
DeCian, J. Fischer, L. Solujic, E. B. Milosavljevic, Organomet-
allics 1992, 11, 401.
Eur. J. Inorg. Chem. 2005, 713–720
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
719

A. M. Z Slawin, J. Wheatley, J. D. Woollins
FULL PAPER
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Received May 27, 2004
Published Online January 27, 2005
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