Synthesis and coordination chemistry of the new unsymmetrical ligand Ph2PCH2NHC6H4PPh2

Article abstract of DOI:10.1002/1099-0682(200207)2002:7<1635::AID-EJIC1635>3.0.CO;2-B

Condensation of Ph₂PCH₂OH with 2-(diphenylphosphanyl)-aniline in toluene gave the new unsymmetrical ligand Ph₂PCH₂NHC₆H₄PPh₂ (1) in good yield. Oxidation of 1 with H₂O₂ or elemental sulfur led to the oxidised products Ph₂P(O)CH₂NHC₆H₄P(O) Ph₂ (2) and Ph₂P(S)CH₂NHC₆H₄P(S) Ph₂ (3). The new ligand 1 demonstrates three distinct modes of coordination. Reaction of compound 1 with [MX₂(cod)] (M = Pd, Pt; X = Cl, Br, Me) or [Mo(CO)₄(pip)₂] gave the chelate complexes [PdCl₂(Ph₂PCH₂NHC₆ H₄PPh₂-P_X,P_A)] (4), [PdBr₂(Ph₂PCH₂NHC₆ H₄PPh₂-P_X,P_A)] (5), [PtCl₂(Ph₂PCH₂NHC₆ H₄PPh₂-P_X,P_A)] (6), [PtMe₂(Ph₂PCH₂NHC₆ H₄PPh₂-P_X,P_A)] (7) and [Mo(CO)₄(Ph₂PCH₂NHC₆ H₄PPh₂-P_X,P_A)] (8). Coordination of 1 with [{RuCl(μCl)(η³:η³-C₁₀ H₁₆)}2] or [{RhCl(μ-Cl)(η⁵-C₅Me₅)}₂] gave the monodentate complexes [RuCl₂(η³:η³-C₁₀ H₁₆)(Ph₂PCH₂NHC₆ H₄PPh₂-P_X)] (9) and [RhCl₂(η⁵-C₅Me₅) (Ph₂PCH₂NHC₆H₄ PPh₂-P_X)] (10). Reaction of 1 with [{IrCl(μ-Cl)(η⁵C₅Me₅)}2] led to a mixture from which the monodentate complex [IrCl₂(η⁵-C₅Me₅) (Ph₂PCH₂NHC₆H₄ PPh₂-P_X)] (11) and the chelate cationic complex [IrCl(η⁵-C₅Me₅) (Ph₂PCH₂NHC₆H₄ PPh₂-P_X,P_A)][Cl] (12) were separated. Abstraction of the chloride ligands from complexes 9 and 10 with AgClO₄ gave the cationic chelate complexes [RuCl(η³:η³-C₁₀H₁₆) (Ph₂PCH₂NHC₆H₄ PPh₂-P_X,P_A)][ClO₄] (13) and [RhCl(η⁵-C₅Me₅)(Ph₂ PCH₂NHC₆H₄PPh₂-P_X, P_A][ClO₄] (14). Compound 1 also functions as a bridging ligand when reacted with two molar equivalents of [AuCl(tht)] or one molar equivalent of [{RhCl(μ-Cl)(η⁵-C₅Me₅)}₂] to give the bimetallic complexes [Ph₂P{AuCl}CH₂NHC₆H₄ PPh₂{AuCl}] (15) and [{RhCl₂(η⁵-C₅ Me₅)}₂(Ph₂PCH₂NHC₆ H₄PPh₂)] (16). The dioxidised compounds 2 and 3 and several typical complexes 8, 9, 11 and 14 were structurally characterised by X-ray diffraction. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

Full text of DOI:10.1002/1099-0682(200207)2002:7<1635::AID-EJIC1635>3.0.CO;2-B

FULL PAPER
Synthesis and Coordination Chemistry of the New Unsymmetrical Ligand
Ph2PCH2NHC6H4PPh2
Qingzhi Zhang,[a] Stephen M. Aucott,[a] Alexandra M. Z. Slawin,[a] and
J. Derek Woollins*[a]
Keywords: Unsymmetrical ligands / Phosphanes / Chelates / Monodentate complexes / Heterometallic complexes
Condensation of Ph2PCH2OH with 2-(diphenylphosphanyl)-
aniline in toluene gave the new unsymmetrical ligand
Ph2PCH2NHC6H4PPh2 (1) in good yield. Oxidation of 1 with
H2O2 or elemental sulfur led to the oxidised products
Ph2P(O)CH2NHC6H4P(O)Ph2 (2) and Ph2P(S)CH2NHC6H4-
P(S)Ph2 (3). The new ligand 1 demonstrates three distinct
plex [IrCl2(η5-C5Me5)(Ph2PCH2NHC6H4PPh2-PX)] (11) and
the chelate cationic complex
[IrCl(η5-C5Me5)(Ph2-
PCH2NHC6H4PPh2-PX,PA)][Cl] (12) were separated. Abstrac-
tion of the chloride ligands from complexes 9 and 10 with
AgClO4 gave the cationic chelate complexes [RuCl(η3:η3-
C10H16)(Ph2PCH2NHC6H4PPh2-PX,PA)][ClO4]
(13)
and
modes of coordination. Reaction of compound
1
with
[RhCl(η5-C5Me5)(Ph2PCH2NHC6H4PPh2-PX,PA][ClO4] (14).
Compound 1 also functions as a bridging ligand when re-
acted with two molar equivalents of [AuCl(tht)] or one molar
equivalent of [{RhCl(µ-Cl)(η5-C5Me5)}2] to give the bimetallic
complexes [Ph2P{AuCl}CH2NHC6H4PPh2{AuCl}] (15) and
[{RhCl2(η5-C5Me5)}2(Ph2PCH2NHC6H4PPh2)] (16). The diox-
idised compounds 2 and 3 and several typical complexes 8,
9, 11 and 14 were structurally characterised by X-ray diffrac-
tion.
[MX2(cod)] (M = Pd, Pt; X = Cl, Br, Me) or [Mo(CO)4(pip)2]
gave the chelate complexes [PdCl2(Ph2PCH2NHC6H4PPh2-
PX,PA)]
[PtCl2(Ph2PCH2NHC6H4PPh2-PX,PA)] (6), [PtMe2(Ph2PCH2-
NHC6H4PPh2-PX,PA)] (7) and [Mo(CO)4(Ph2PCH2-
(4),
[PdBr2(Ph2PCH2NHC6H4PPh2-PX,PA)]
(5),
NHC6H4PPh2-PX,PA)] (8). Coordination of 1 with [{RuCl(µ-
Cl)(η3:η3-C10H16)}2] or [{RhCl(µ-Cl)(η5-C5Me5)}2] gave the
monodentate
complexes
[RuCl2(η3:η3-C10H16)(Ph2-
PCH2NHC6H4PPh2-PX)] (9) and [RhCl2(η5-C5Me5)(Ph2PCH2-
NHC6H4PPh2-PX)] (10). Reaction of 1 with [{IrCl(µ-Cl)(η5-
C5Me5)}2] led to a mixture from which the monodentate com-
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
2002)
Introduction
between the NH and the PPh2 moieties giving the ligand
a flexible PCNC2P spine. Other rare literature examples
of PCNC2P backboned ligand systems include
diphenyl[3-(2-diphenylphosphanylphenylsydonyl)-
phosphane[19] A, the substituted quinazolinone ligand B[20]
and the bis(diphenylphosphanyl)- and bis(dicyclohexyl-
Chemically symmetrical bisphosphane ligands have been
intensively investigated in all aspects of inorganic and or-
ganometallic chemistry, and Ph2PCH2PPh2 [bis(diphenyl-
phosphanyl)methane (dppm)], Ph2PCH2CH2PPh2 [bis(di-
phenylphosphanyl)ethane (dppe)], and its -(CH2)n- back-
boned homologues, the aromatic Ph2PC6H4PPh2 [1,2-phen-
ylenebis(diphenylphosphane)] and the ferrocene backboned
1,1Ј-bis(diphenylphosphanyl)ferrocene are all well-known
examples of this class of ligand.[1Ϫ9] Unsymmetric bisphos-
phanes, with the notable exception of chiral aminophos-
phane-phosphinites,[10] have received relatively little atten-
tion (for recent examples see refs.[11Ϫ15]). We recently de-
scribed the synthesis of Ph2PC6H4NHPPh2 an unsymmet-
rical diphosphane derived from 2-(diphenylphosphanyl)-
aniline[16] in which the two phosphorus atoms demonstrated
different coordination activities.[17,18] Herein we report
another unsymmetrical diphosphane Ph2PCH2NHC6-
H4PPh2 which has an additional methylene spacer group
phosphanyl)pyrrole-derived diphosphanes
C
and D[21]
(Scheme 1). The synthesis of Ph2PCH2NHC6H4PPh2 and
its reactivity towards a variety of late transition metals are
described. The products from these reactions have been
characterised principally by multi-element NMR spectro-
scopy and X-ray crystallography.
Results and Discussion
Preparation and Characterisation of the Ligand
The condensation of equimolar quantities of diphenylph-
osphanylmethanol and 2-(diphenylphosphanyl)aniline in
toluene at 90Ϫ95 °C gave the unsymmetrical bisphosphane
Ph2PC6H4NHCH2PPh2 (1) in excellent yield (84.4%)
(Scheme 2). The white solid product was stable to moisture
and air. The 31P{1H} NMR spectrum of 1 in CDCl3 shows
two distinct singlets at δP ϭ Ϫ18.77 and δP ϭ Ϫ22.30. Al-
though it is not easy to assign the signals in reference to
[a]
Department of Chemistry, University of St Andrews, Fife,
Scotland KY16 9ST, UK
Fax: (internat.) ϩ 44-1334/463-384
E-mail: jdw3@st-and.ac.uk
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 1434Ϫ1948/02/0707Ϫ1635 $ 20.00ϩ.50/0
1635

Q. Zhang, S. M. Aucott, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
Compound 2 was prepared by the oxidation of 1 with H2O2
and compound 3 by oxidation of 1 with elemental sulfur.
Compounds 2 and 3, like their parent compound 1, gave
good microanalysis and the expected FAB-MS spectral pat-
terns. The 31P{1H} NMR spectrum of 2 (in CD2Cl2) ex-
hibits two singlets at higher frequency than those of 1. The
singlet at δP ϭ 36.38 was assigned to the triarylphosphane
(PA) and that at δP ϭ 28.58 to the phosphorus (PX) of the
NHCH2PPh2 moiety by comparison with the signals of
compounds 23 and 24 (Scheme 4, Table 3). The two singlets
of compound 3 at δP ϭ 39.35 and 38.46 in CD2Cl2 were
too close to be assigned unambiguously, but we have as-
signed the singlet at δP ϭ 39.35 to the triarylthiophosphi-
noyl (PA) and that at δP ϭ 38.46 to the NHCH2P(S)Ph2
moiety (PX) by comparing the signals with those of com-
pounds 25 and 26 (Scheme 4, Table 3). The synthesis and
complex formation of compounds 23Ϫ26 in Scheme 4 will
be reported elsewhere.
Scheme 1. Examples of PCNC2P backboned ligands
the starting reactant 2-(diphenylphosphanyl)aniline[16] (17)
or the previously reported Ph2PNHC6H4PPh2
[17]
1
(18)
The H NMR spectra of 2 and 3 show similar aromatic
(Scheme 2, Table 1), the resonance at δP ϭ Ϫ18.77 was as-
signed to the phosphorus (PX) of the NHCH2PPh2 group
and the other signal at δP ϭ Ϫ22.30 to the triarylphosphane
moiety (PA) by comparing the 31P{1H} NMR spectra of its
monodentate complexes 9Ϫ11, which will be discussed be-
low. These assignments are also in accordance with those
in other reported molecules (19Ϫ22)[22Ϫ25] shown below
(Scheme 3, Table 1).
proton signals to that of 1. However, the NH resonance in
2 was obscured by the aromatic proton resonances; the 1H-
1H COSY spectrum reveals that the NH signal lies at ca.
δH ϭ 7.30. In compound 3 the NH signal was confirmed
by an H/D exchange reaction. In both cases, the NH reson-
ances are shifted to higher frequency by ca. 2 ppm relative
to 1. In the IR spectra, the νNH absorption was also shifted
to lower frequency by 30 cmϪ1 for 2 and 138 cmϪ1 for 3.
This is attributed to the intramolecular hydrogen bonding
interactions that occur in compounds 2 and 3, as seen in
the crystal structures.
In the solid state, 2 and 3 (Figure 1a and 2, respectively)
both form an envelope-like pseudo six-membered ring via
intramolecular hydrogen bonding interactions between the
Scheme 2. Preparation of ligand 11
H(13n) and the O(2) or S(2) at P(2). The O(2) atom in com-
˚
pound
2
is
0.60
A
out
of
the
P(2)Ϫ
Table 1. 31P{1H} NMR chemical shifts of 1, and related com-
pounds 17Ϫ22
C(15)ϪC(14)ϪH(13n)ϪN(13) mean plane (mean deviation
of 0.07 A) with a fold angle of 32°. In compound 3, the
˚
deviation of S(2) from the P(2)ϪC(15)ϪC(14)Ϫ
H(13n)ϪN(13) mean plane (mean deviation from each
Chemical shifts
Chemical shifts
Compound δ(PX)[a] δ(PA)[a] Compound δ(PX)[a] δ(PA)[a]
˚
˚
other 0.05 A) of Ϫ1.27 A is bigger than that in compound
2 due to the different bond lengths of PϭO and PϭS
(Table 2), as well as the strength of the H bonding
1
Ϫ18.77 Ϫ22.30 20[b]
Ϫ16.8
Ϫ17.9
Ϫ
Ϫ
Ϫ
Ϫ21.5
17[b]
18[b]
19[b]
Ϫ
29.6
Ϫ19.75 21[b]
Ϫ19.5
22[b]
˚
[H(13n)···O(2): 1.98 A; O(2)···H(13n)ϪN(13): 144°;
Ϫ18.16
Ϫ
˚
H(13n)···S(2): 2.47 A; S(2)···H(13n)ϪN(13): 144°]. The
[a]
hinge angle between the S(2)ϪP(2)ϪH(13) plane and the
P(2)ϪC(15)ϪC(14)ϪH(13n)ϪN(13) mean plane along the
P(2)ϪH(13n) axis is 46°. In addition to the intramolecular
hydrogen bonding, compounds 2 and 3 share other com-
mon features: the two PϭE (E ϭ O, S) groups lie in an anti-
PX is the phosphorus of either NHCH2PPh2 or NHPPh2 groups
and PA is the phosphorus of triarylphosphane.
pounds.
[b]
Literature com-
In the 1H NMR spectrum, the resonances of the aromatic position; the geometry around each phosphorus atom is ap-
protons are found between δH ϭ 7.40 and 6.64. The NH proximately tetrahedral; the main skeleton of molecules 2
proton appears as a broad singlet at δH ϭ 4.97. The triplet and 3 — P(2)ϪC(15)ϪC(14)ϪN(13)ϪC(13) — lies in a
˚
˚
at δH ϭ 3.83 was assigned to the methylene group, with mean plane with a mean deviation of 0.04 A and 0.02 A,
equal couplings (3JP,CH ϭ JCH,NH ϭ 5 Hz). The infrared respectively. The planar skeleton can be explained from the
3
spectrum of 1 shows νNH at 3345 cmϪ1. Attempts to grow sp2 hybrid state of C(15) and C(14) as well as the conjuga-
crystals of 1 suitable for X-ray analysis were not successful. tion of N(13) with the aromatic ring. The
However, the structures of its oxidised counterparts 2 (Fig- C(14)ϪN(13)ϪC(13) bond angle is 124.5(4)° and 126.0(2)°
ure 1, Table 2) and 3 (Figure 2, Table 2) were obtained. in 2 and 3, respectively. There is one additional feature in
1636
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646

The New Unsymmetrical Ligand Ph2PCH2NHC6H4PPh2
FULL PAPER
Scheme 3. Compound 1 and other related molecules
˚
Table 2. A comparison of the bond lengths (A) and angles (°) in
compounds 2 and 3
2
3
P(1)ϪE(1)
1.483(4)
1.812(5)
1.450(6)
1.383(6)
1.414(6)
1.808(5)
1.487(3)
1.9443(12)
1.833(3)
1.447(3)
1.378(4)
1.428(4)
1.818(3)
1.9717(11)
P (1)ϪC(13)
N(13)ϪC(13)
N(13)ϪC(14)
C(14)ϪC(15)
C(15)ϪP(2)
P(2)ϪE(2)
E(1)ϪP(1)ϪC(13)
N(13)ϪC(13)ϪP(1)
C(14)ϪN(13)ϪC(13)
N(13)ϪC(14)ϪC(15)
C(14)ϪC(15)ϪP(2)
E(2)ϪP(2)ϪC(15)
112.6(2)
110.5(3)
124.5(4)
119.0(4)
120.5(4)
112.4(2)
113.95(11)
112.0(2)
126.0(2)
119.7(2)
121.1(2)
114.34(10)
Figure 1. (a) Crystal structure of Ph2P(O)CH2NHC6H4P(O)Ph2
(2): a single molecule; (b) crystal structure of Ph2P(O)CH2NHC6-
H4P(O)Ph2 (2) showing the hydrogen bonded dimer pairs
compound 2 (Figure 1b) that is not observed in compound
3: each molecule of 2 crystallises with 0.5 molecules of
water. The water links two molecules of 2 through weak
intermolecular hydrogen bonding interactions with the oxy-
gen atom of the NCH2P(O)Ph2 moiety and O(1) and O(1A)
Figure 2. Crystal structure of Ph2P(S)CH2NHC6H4P(S)Ph2 (3)
Coordination Chemistry of Compound 1
˚
[O(1)···H(40o): 2.49 A; O(1)···H(40o)ϪO(40): 102°]. There-
Both of the phosphorus atoms of 1 can coordinate with
fore, it is not surprising to see that there is little difference late transition metals. When reacted with PdII, PtII or Mo0,
˚
between the two PϭO bond lengths [P(1)ϪO(1): 1.487(3) A; 1 functions as a bidentate ligand to give the seven-mem-
˚
P(2)ϪO(2): 1.483(4) A] in compound 2, while, in contrast, bered chelate complexes 4Ϫ8 (Scheme 5). However, due to
˚
P(2)ϪS(2) [1.9719(11) A] is longer than P(1)ϪS(1) their different chemical environments the reactivity of the
˚
[1.9443(12) A] in 3.
two phosphorus atoms is different. The less bulky and less
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646
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Q. Zhang, S. M. Aucott, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
electron-delocalized phosphorus (PX) of the NHCH2PPh2
group is more reactive than triarylphosphane (PA). When 1
reacts with RhIII/RuIV chloride-bridged dimers in a 2:1
molar ratio, the ‘‘dangling’’ monodentate complexes 9 and
10 were obtained (Scheme 5). However, reaction of 1 with
[{IrCl(µ-Cl)(η5-C5Me5)}2] in a 2:1 molar ratio led to the
cationic chelate complex 12 together with monodentate 11.
Abstraction of chloride from 9 and 10 with silver perchlor-
ate gave the cationic chelate complexes 13 and 14. When
[AuCl(tht)] was employed, both (PX) and (PA) in 1 coordin-
ate to the gold centre. We believe that steric effects control
the reaction. Changing the reactants molar ratio also
change the products: when two molar equivalents of
[AuCl(tht)] or one molar equivalent of [{RhCl(µ-Cl)(η5-
C5Me5)}2] was reacted with ligand 1, the bidentate bridging
complexes 15 and 16 were obtained (Scheme 5).
Scheme 4. Compounds related to 2 and 3
Table 3. 31P{1H} NMR chemical shifts of 2, 3 and related com-
pounds
Bidentate Chelate Complexes
Chemical shifts
Chemical shifts
Reactions of equimolar quantities of ligand 1 and
[PdCl2(cod)], [PdBr2(cod)], [PtCl2(cod)], [PtMe2(cod)] or
[Mo(CO)4(pip)2] gave the corresponding seven-membered
ring chelate complexes [PdCl2(Ph2PCH2NHC6H4PPh2-
PX,PA)] (4), [PdBr2(Ph2PCH2NHC6H4PPh2-PX,PA)] (5),
[PtCl2(Ph2PCH2NHC6H4PPh2-PX,PA)] (6), [PdMe2(Ph2-
PCH2NHC6H4PPh2-PX,PA)] (7) and [Mo(CO)4(Ph2-
PCH2NHC6H4PPh2-PX,PA)] (8), respectively. All of the
Compound δ(PX)[a] δ(PA)[a] Compound δ(PX)[a] δ(PA)[a]
2
3
28.58 36.38
38.46 39.35
Ϫ19.90 36.59
24[a]
25[a]
26[a]
27.82 39.98
Ϫ20.46 39.67
38.32 36.60
[a]
23
[a] PX is the phosphorus of NHCH2PPh2 groups and PA is the phos-
phorus of triarylphosphane.
Scheme 5. (i) [MX2(cod)] (M ϭ Pd, X ϭ Cl or Br; M ϭ Pt, X ϭ Cl or Me); (ii) [Mo(CO)4(pip)2]; (iii) 0.5 equiv. of [{RuCl(µ-Cl)(η3:η3-
C10H16)}2] or [{RhCl(µ-Cl)(η5-C5Me5)}2]; (iv) 0.5 equiv. of [{IrCl(µ-Cl)(η5-C5Me5)}2]; (v) AgClO4; (vi) 2 equiv. of [AuCl(tht)]; (vii)
[{RhCl(µ-Cl)(η5-C5Me5)}2]
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Eur. J. Inorg. Chem. 2002, 1635Ϫ1646

The New Unsymmetrical Ligand Ph2PCH2NHC6H4PPh2
FULL PAPER
complexes gave satisfactory microanalysis and the expected
fragmentation patterns in their positive ion FAB mass spec-
tra. In the 31P{1H} NMR spectra of 4 and 5 no 31P-31P
coupling was observed, both compounds displayed two
singlets at around δP ϭ 42 and δP ϭ 21. The 31P{1H} NMR
spectra of the platinum complex 6 exhibited a two-bond
31P-31P coupling and the expected platinum satellites at
Table 4. Chemical shifts of complexes 4؊8 and those from
Ph2PNHC6H4PPh2
Chemical shifts
Chemical shifts
Complex
δ(PX)[a]
δ(PA)[a]
Complex
δ(PX)[a]
δ(PA)[a]
8
4
5
6
7
41.43
42.72
41.93
20.25
30.73
28.31
22.98
20.55
1.80
27[b]
28[b]
91.7
77.8
33.6
18.1
1
2
δP ϭ 20.25 (d, JPt,P ϭ 3647 Hz, JP,P ϭ 18 Hz) and δP ϭ
29[b]
30[b]
53.8
70.6
Ϫ0.4
10.7
1
2
1.80 (d, JPt,P ϭ 3573, JP,P ϭ 18 Hz). The large one-bond
31P-195Pt coupling constants are in agreement with the pro-
posed cis-geometry of 6. In compound 7, two doublets at
11.91
[a]
PX is the phosphorus of either NHCH2PPh2 or NHPPh2 groups
δP ϭ 30.73 and 11.91 (2JP,P ϭ 12 Hz) with platinum satel- and PA is the phosphorus of triarylphosphane. Literature com-
[b]
plexes.[8]
lites are observed. The coupling constants 1JPt,P ϭ 1853 Hz
1
and JPt,P ϭ 1720 Hz are in agreement with those coupling
constants found in compounds in which phosphane ligands coupling constants 2JP,CH ϭ 3 Hz and 3JNH,CH ϭ 6 Hz were
are trans to methyl groups. The molybdenum complex 8 determined by an exchange reaction with D2O.
1
also displays coupling of the two phosphorus atoms at δP ϭ
In the H NMR spectrum of complex 7, the NH and
41.43 and δP ϭ 28.31 (2JP,P ϭ 25 Hz) in the 31P{1H} NMR CH2 resonances overlap at δH ϭ 3.99. Addition of D2O to
spectrum. The assignment of the phosphorus resonances in the CDCl3 solution of 7 gives a 2JP,CH coupling constant of
the above chelate complexes is not straightforward. How- 9 Hz. Other information obtained from this compound is
ever, by comparing them with the corresponding complexes the two doublets of doublets at δH ϭ 0.60 and 0.34 with
[18]
of PPh2C6H4NHPPh2
(Scheme 6, Table 4), we assigned platinum satellites for two CH3 groups. Although the coup-
the signal at higher frequency in the 31P{1H} NMR spectra ling constants are available (3JP,CH ϭ 7, JPЈ,CH ϭ 9,
3
of each chelate complex to the phosphorus of the 2JPt,CH ϭ 70, JPt,CHЈ ϭ 69 Hz) the accurate assignment of
2
NHCH2PPh2 group (PX) and the lower frequency reson- the two doublets is impossible. The resonance for the NH
ance to the triarylphosphane (PA). The 1H NMR spectra of proton in complex 8 was obscured by aromatic multiplets.
4Ϫ8 show similar patterns for the aromatic proton reson- The CH2 group in 8 appears as a broad singlet at δH ϭ 4.04.
ances, although the NH and CH2 signals are slightly differ-
In the infrared spectra, compounds 4, 5 and 6 show the
ent depending upon the nature of the solvent and the com- νNH absorption at around 3250 cmϪ1, shifted to lower fre-
plexes. The NH resonances of 4 and 5 appear as broad quency relative to 1. Metal-halide stretches at ca. 320 cmϪ1
doublets of triplets in [D6]DMSO at δH ϭ 5.53 (3JPN,CH
ϭ
and 290 cmϪ1 are in agreement with the cis-geometry of the
3
10, JNH,CH ϭ 3 Hz) and δH ϭ 5.44 (3JPN,CH ϭ 25, complexes. However, the νNH absorption at 3337 cmϪ1 in
3JNH,CH ϭ 3 Hz), respectively. Their CH2 signals were compound 7 and 3389 cmϪ1 in 8 occurs at a significantly
found at ca. δH ϭ 3.9 as a triplet (2JP,CH
ϭ
3JNH,CH
ϭ
higher frequency than in 4Ϫ6. Obviously there is less op-
portunity for hydrogen bonding between the NH proton of
the ligand and the methyl or carbonyl groups of 7 and 8,
respectively, than between the metal-bound chlorides and
the amine protons of complexes 4Ϫ6. The infrared spec-
trum of compound 8 also displayed νCϵO absorption bands
3 Hz).
at 2013 cmϪ1, 1914 cmϪ1, 1892 cmϪ1 and 1878 cmϪ1
.
Pale yellow crystals of 8 suitable for X-ray analysis (Fig-
ure 3, Table 5) were obtained by layering methanol onto a
dichloromethane solution of 8 for four days. As shown in
Figure 3, the coordination geometry around Mo(1) is ap-
proximately octahedral, with P(1) and P(2) occupying the
cis positions. The bite angle of the ligand is 87.47(2)°,
slightly less than the expected 90° for a regular octahedron.
The cis bond angles at Mo(1) are 84.29(2)Ϫ91.51(11)°,
while
the
trans
angle
are
in
the
range
172.59(10)Ϫ176.66(8)°. The seven-membered chelate ring is
twisted, with N(13)ϪC(14)ϪC(15)ϪP(1)ϪP(2) coplanar
˚
˚
(mean deviation 0.01 A) and C(13) lying 0.96 A above, and
˚
Scheme 6. Chelate complexes of 1 and Ph2NHC6H4PPh2
Mo(1) 1.49 A below, the mean plane. The fold angles be-
tween the N(13)ϪC(14)ϪC(15)ϪP(1)ϪP(2) mean plane
1
In the H NMR spectrum of 6, the doublet of triplets and the N(13)ϪC(13)ϪP(1) and P(2)ϪMo(1)ϪP(1) planes
signal of NH was observed at δH ϭ 3.55 (3JNH,CP ϭ 16 Hz). are 54° and 88° respectively. The N(13)ϪC(14)ϪC(15)
The doublet of doublets with two platinum satellites [124.7(2)°] and C(14)ϪC(15)ϪP(2) [124.6(2)°] bond angles
(3JPt,CH ϭ 36 Hz) at δH ϭ 3.96 was assigned to CH2. The are slightly more open than those in compounds 2 and 3.
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646
1639

Q. Zhang, S. M. Aucott, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
˚
Table 5. Selected bond lengths (A) and angles (°) for compound 8
Mo(1)ϪC(41)
Mo(1)ϪC(43)
Mo(1)ϪP(1)
P (1)ϪC(13)
N(13)ϪC(14)
C(15)ϪP(2)
2.041(3)
2.021(3)
2.5048(6)
1.847(2)
1.401(3)
1.856(2)
Mo(1)ϪC(42)
Mo(1)ϪC(44)
Mo(1)ϪP(2)
N(13)ϪC(13)
C(14)ϪC(15)
1.992(3)
1.985(3)
2.5884(6)
1.460(3)
1.414(3)
C(41)ϪMo(1)ϪC(42)
C(41)ϪMo(1)ϪC(44)
C(42)ϪMo(1)ϪC(44)
C(41)ϪMo(1)ϪP(1)
C(43)ϪMo(1)ϪP(1)
C(41)ϪMo(1)ϪP(2)
C(43)ϪMo(1)ϪP(2)
P(1)ϪMo(1)ϪP(2)
N(13)ϪC(13)ϪP(1)
N(13)ϪC(14)ϪC(15)
C(15)ϪP(2)ϪMo(1)
87.97(10)
91.51(11)
90.79(11)
94.78(7)
91.12(7)
87.00(8)
97.74(8)
87.47(2)
107.9(2)
124.7(2)
119.01(7)
C(41)ϪMo(1)ϪC(43)
C(42)ϪMo(1)ϪC(43)
C(43)ϪMo(1)ϪC(44)
C(42)ϪMo(1)ϪP(1)
C(44)ϪMo(1)ϪP(1)
C(42)ϪMo(1)ϪP(2)
C(44)ϪMo(1)ϪP(2)
C(13)ϪP(1)ϪMo(1)
C(14)ϪN(13)ϪC(13)
C(14)ϪC(15)ϪP(2)
172.59(10)
85.99(11)
84.29(11)
176.66(8)
87.25(7)
94.58(8)
174.38(8)
112.36(7)
122.6(2)
124.6(2)
coordinated phosphorus resonance shifted to higher fre-
quency and that of the dangling phosphorus at ca. δP
Ϫ22.5 unmoved. For the rhodium complex 10, a typical
1JRh-P coupling constant of 141 Hz was observed at δP
ϭ
ϭ
32.74. The higher-frequency signal was assigned to the
phosphorus of the NHCH2PPh2 group (PX) and the un-
shifted δP ϭ Ϫ22.5 to triarylphosphane (PA). This assign-
ment was confirmed by single-crystal X-ray diffraction
studies of complexes 9 and 11 (see below).
The 1H NMR spectra of 9Ϫ11 show aromatic proton res-
onances close to the values for the free ligand. The signals
for the NH and methylene protons of the complexes are
slightly different. Complexes 10 and 11 display a slightly
broad quadruplet for NH at ca. δH ϭ 4.9 (3JNH,CH
ϭ
3JNH,CP ϭ 7 Hz) and a doublet at δH ϭ 4.48Ϫ4.66 for CH2.
No coupling between the CH2 protons and the phosphorus
was observed. In complex 9, the NH proton signal is a well-
resolved multiplet at δH ϭ 4.95. The CH2 group was ob-
served as a doublet of doublets at δH ϭ 4.59. The coupling
constants were verified by H/D exchange with D2O
Figure 3. Crystal structure of [Mo(CO)4(Ph2PCH2NHC6H4PPh2-
PX,PA)] (8)
Monodentate Complexes
Monitoring of the reaction between 1 and either
[{RuCl(µ-Cl)(η3:η3-C10H16)}2] or [{RhCl(µ-Cl)(η5-C5-
Me5)}2] by 31P{1H} NMR spectroscopy showed that
the monodentate complexes [RuCl(η3:η3-C10H16)(Ph2-
PCH2NHC6H4PPh2-PX)] (9) and [RhCl(η5-C5Me5)(Ph2-
PCH2NHC6H4PPh2-PX)] (10) are readily formed. The reac-
tion of [{IrCl(µ-Cl)(η5-C5Me5)}2] and 1, however, is not so
straightforward. Several singlets between δP ϭ 0.0 and δP ϭ
Ϫ22 appear in the crude reaction mixtures. Longer reaction
times do not affect the product distribution. After several
3
(2JP,CH ϭ 2, JNH,CH ϭ 6 Hz). Complexes 10 and 11 show
coupling between (PX) and the methyl protons of the penta-
methylcyclopentadienyl group, [JP···CH ϭ 3 Hz]. The com-
1
plicated signals of complex 9 were also assigned by a H-
1H COSY spectrum. The IR spectra of 9Ϫ11 show the νNH
absorption at about 3320 cmϪ1, implying little hydrogen
bonding.
Slow evaporation of a dichloromethane solution of 9 gave
attempts to separate this mixture a monodentate complex well-formed deep purple crystals suitable for X-ray analysis.
[IrCl(η5-C5Me5)(Ph2PCH2NHC6H4PPh2-PX)] (11) was isol- The crystal structure of 9 (Figure 4, Table 6) reveals a mono-
ated as well-formed crystals from dichloromethane/acetone dentate complex coordinated by the NHCH2PPh2 phos-
in low yield. Also obtained was the chelate cationic complex phorus atom, whilst the triarylphosphane moiety remains
[Ir(η5-C5Me5)(Ph2PCH2NHC6H4PPh2-PX,PA)] (12), al- unbound. The Ru(1) centre adopts an approximately tri-
though in much lower purity.
gonal bipyramidal geometry with Cl(1) and Cl(2) occupy-
All of the monodentate complexes gave satisfactory mic- ing the axial sites while P(1) and the two allylic groups oc-
roanalysis and the expected fragmentation patterns and mo- cupy the equatorial positions. The arrangement of the al-
lecular ions in the positive ion FAB mass spectra. Com- lylic groups, which have local C2 symmetry, is similar to
pound 9Ϫ11 have similar 31P{1H} NMR spectra, with the that found in related complexes.[26] The ligand backbone
1640
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646

The New Unsymmetrical Ligand Ph2PCH2NHC6H4PPh2
FULL PAPER
P(2)ϪC(15)ϪC(14)ϪN(13), as observed in 2, 3, and 8, is enyl top. The bond angles between the ‘‘legs’’ are approxim-
˚
coplanar (mean deviation 0.01 A). The dangling phos- ately 90°.
phorus P(2) remains pyramidal as expected.
Figure 4. Crystal structure of [RuCl2(η3:η3-C10H16)(Ph2-
PCH2NHC6H4PPh2-PX)] (9)
Figure
5.
Crystal
structure
of
[IrCl2(η5-C5Me5)(Ph2-
PCH2NHC6H4PPh2-PX)] (11)
˚
Table 6. A comparison of the bond lengths (A) and angles (°) in
compounds 9 and 11
Cationic Chelate Complexes
As mentioned above, a cationic chelate complex of iri-
dium(III) 12 formed together with the monodentate species
11. Other cationic chelate complexes of ligand 1 can be ob-
tained by abstraction of a chloride ligand from the monod-
entate complexes. For example, abstraction of one chloride
from complexes 9 and 10 with AgClO4 gave the chelate
9
11
M(1)ϪP(1)
M(1)ϪCl(1)
M(1)ϪCl(2)
P(1)ϪC(13)
N(13)ϪC(13)
N(13)ϪC(14)
C(14)ϪC(15)
C(15)ϪP(2)
P(2)ϪC(20)
P(2)ϪC(26)
2.393(4)
2.413(4)
2.387(4)
1.862(11)
1.399(14)
1.379(15)
1.364(16)
1.798(12)
1.810(16)
1.801(13)
2.2986(13)
2.4119(15)
2.4035(16)
1.833(6)
1.457(7)
1.384(7)
1.415(8)
1.825(6)
1.831(6)
1.830(6)
cationic
complexes
[RuCl(η3:η3-C10H16)(Ph2PCH2-
(13) and
[RhCl(η5-
NHC6H4PPh2-PX,PA)][ClO4]
C5Me5)(Ph2PCH2NHC6H4PPh2-PX,PA)][ClO4] (14), re-
spectively. Both complexes gave satisfactory microanalysis
and positive FAB mass spectra. Their IR spectra displayed
the νNH at 3272 cmϪ1 and 3332 cmϪ1, respectively, and the
strong band of ClO4Ϫ at ca. 1095 cmϪ1. The 31P{1H} NMR
spectrum of 13 showed two singlets at δP ϭ 36.89 and δP ϭ
21.86 in CDCl3, which were assigned to the phosphorus
atoms of the NHCH2PPh2 (PX) and the triarylphosphane
(PA) groups, respectively, by reference to the other chelate
Cl(1)ϪM(1)ϪCl(2)
Cl(1)ϪM(1)ϪP(1)
Cl(2)ϪM(1)ϪP(1)
M(1)ϪP(1)ϪC(13)
N(13)ϪC(13)ϪP(1)
C(14)ϪN(13)ϪC(13)
N(13)ϪC(14)ϪC(15)
C(14)ϪC(15)ϪP(2)
C(20)ϪP(2)ϪC(15)
C(20)ϪP(2)ϪC(26)
C(15)ϪP(2)ϪC(26)
172.84(15)
89.25(13)
84.01(13)
114.4(4)
111.0(8)
123.7(11)
120.2(12)
118.8(10)
102.4(6)
101.1(7)
103.4(6)
88.86(6)
88.27(5)
88.04(5)
112.50(19)
112.3(4)
123.9(5)
119.3(5)
117.8(4)
104.0(3)
102.2(3)
102.2(3)
1
complexes mentioned above. The H NMR spectrum of 13
showed a broad singlet at δH ϭ 5.02 for NH and a doublet
of doublet of doublets at δH ϭ 4.67 for the ligand methylene
3
3
2
protons with JNH,CH ϭ 6, JP,CH ϭ 15 Hz and JP,CH
ϭ
52 Hz. Characterisation of 14 by multinuclear NMR proved
unsuccessful. The 31P{1H} NMR spectrum of 14 exhibited
very broad peaks around δP ϭ 31 and δP ϭ 37, and the
The X-ray structure of 11 (Figure 5) shares many com- 1H NMR spectrum of this compound also contains broad
mon features with 9: the pendant triarylphosphane P(2) ad- resonances. The low solubility of 14 in common organic
opts a pyramidal geometry; the main backbone of the li- solvents precludes a low temperature NMR study. In solu-
gand extends in a mean plane P(2)ϪC(15)ϪC(14)ϪN(13) tion we believe that there may be an exchange process be-
˚
(mean deviation 0.06 A); the bond lengths and angles tween several species taking place, possibly the cationic che-
(Table 6) are in the expected range; no hydrogen bonding is late, a monodentate species and perhaps even a cationic bi-
observed. The geometry around Ir(1) can be viewed as a dentate bridging species.
three-legged ‘‘piano stool’’ with the two chlorides and the
In spite of the uninformative NMR spectroscopic data
phosphorus P(1) supporting the pentamethylcyclopentadi- we were able to obtain single crystals of compound 14 enab-
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646
1641

Q. Zhang, S. M. Aucott, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
ling characterisation by X-ray crystallography (Figure 6, Bimetallic Complexes
Table 7). The crystal structure of 14 reveals that the com-
While the RuIV or RhIII metal centres of the bulky dimers
plex adopts a chair-like seven-membered chelate ring with
a ligand bite angle P(1)ϪRh(1)ϪP(2) of 95.12(4)°. The top
mean plane of the ‘‘chair’’, C(14)ϪC(15)ϪP(2)ϪN(13)
[{RuCl(µ-Cl)(η3:η3-C10H16)}2]
and
[{RhCl(µ-Cl)(η5-
C5Me5)}2] selectively coordinate through the (PX) or
NHCH2PPh2 moiety of ligand 1, [AuCl(tht)] displays no
such selectivity for either (PA) or (PX) of ligand 1. The reac-
tion between [AuCl(tht)] and 1 in a 1:1 ratio showed two
broad peaks at δP ϭ 33.4 and 25.0 in the 31P{1H} NMR
spectrum, implying that both (PX) and (PA) were involved
in some type of coordination. Workup of this mixture was
not attempted. Addition of one more molar equivalent of
[AuCl(tht)] to this mixture led to the same bidentate
bridging complex 15 as in the one step reaction of
[AuCl(tht)] with 1 in a 2:1 molar ratio. Complex 15 exhibits
two sharp singlets at δP ϭ 24.95 and δP ϭ 18.64 which are
assigned to (PX) of the NHCH2PPh2 group and the (PA) of
the triarylphosphane according to the general trend of the
˚
(mean deviation 0.02 A), is 123° folded back from the
‘‘back of the chair’’, N(13)ϪP(2)ϪC(13)ϪRh(13) mean
˚
plane (mean deviation 0.12 A). The ‘‘bottom of the chair’’,
P(1)ϪRh(1)ϪC(13), is 144° folded forward from the
N(13)ϪP(2)ϪC(13)ϪRh(13) mean plane. Again, the coor-
dination around the rhodium adopts a three-legged ‘‘piano
stool’’ geometry. The crystal structure also displays two
weak hydrogen bonding interactions between the NH and
Ϫ
two of the oxygen atoms of the tetrahedral ClO4 anion
˚
˚
[H(13n)···O(1): 2.42 A; H(13n)···O(3): 2.44 A;
N(13)ϪH(13n)···O(1): 145°; N(13)ϪH(13n)···O(3): 157°].
The crystal structure also reveals that each molecule of
complex 14 crystallises with 0.25 molecules of dichlorome-
thane.
1
complexes discussed in this paper. The H NMR spectrum
of 15 showed a well-resolved and well-shaped multiplet at
δH ϭ 4.94 for the NH proton and a doublet of doublets at
1
δH ϭ 4.34 for CH2. A H-1H COSY spectrum of the com-
pound in CDCl3 showed no coupling between the NH and
aromatic proton 6-H. Therefore it was concluded that both
of the phosphorus atoms coupled with the NH group. The
coupling constants were obtained through a D2O exchange
3
reaction in CDCl3 solution (2JP,CH ϭ 3, JNH,CH ϭ 6,
4
3JPC,NH ϭ JPCCNH ϭ 3 Hz).
The reaction of [{RhCl(µ-Cl)(η5-C5Me5)}2] with 1 in a
1:1 molar ratio gave another bimetallic complex
[{RhCl2(η5-C5Me5)}2(Ph2PCH2NHC6H4PPh2)] (16). The
31P{1H} NMR spectrum of 16 displays two doublets at
δP ϭ 32.44 (1JRh,P ϭ 138 Hz) and δP ϭ 27.79 (1JRh,P
ϭ
144 Hz). Upon comparison with the 31P{1H} NMR spec-
trum of 9, the doublet at δP ϭ 32.44 was assigned to the
NHCH2PPh2 group (PX), and the other at δP ϭ 27.79 to
1
the triarylphosphorus atom (PA). The H NMR spectrum
of 16 displayed two doublets for the two pentamethylcyclo-
pentadienyl groups. The NH resonance appears at δH
ϭ
5.33 as a broad triplet and that of the ligand methylene
protons at δH ϭ 4.90 as a broad doublet of doublets
of [RhCl(η5-C5Me5)(Ph2-
2
(3JNH,CH ϭ 5, JP,CH ϭ 16 Hz). Both bridging complexes
Figure 6.
Crystal structure
PCH2NHC6H4PPh2-PX,PA][ClO4] (14); the solvent of crystallis-
gave satisfactory microanalysis and the anticipated FAB
mass spectral patterns. Their IR spectra show vibrations for
νNH at 3309 and 3280 cmϪ1 and νM-Cl at 329 and 398
cmϪ1, respectively.
ation is omitted for the sake of clarity
˚
Table 7. Selected bond lengths (A) and angles (°) in compound 14
Conclusion
Rh(1)ϪP(1)
Rh(1)ϪCl(1)
N(13)ϪC(13)
C(14)ϪC(15)
2.3303(12) Rh(1)ϪP(2)
2.4016(12) P (1)ϪC(13)
2.3806(11)
1.854(4)
1.414(6)
1.836(4)
We have shown that the unsymmetrical bisphosphane li-
gand Ph2PCH2NHC6H4PPh2 is readily prepared by the
condensation of diphenylphosphanylmethanol (Ph2PCH2-
OH) and 2-(diphenylphosphanyl)aniline (Ph2PC6H4NH2),
and that treatment of Ph2PCH2NHC6H4PPh2 with H2O2 or
elemental sulfur gives rise to the dioxide and disulfide. In
1.452(6)
1.389(6)
N(13)ϪC(14)
C(15)ϪP(2)
P(1)ϪRh(1)ϪP(2)
P(2)ϪRh(1)ϪCl(1)
N(13)ϪC(13)ϪP(1)
N(13)ϪC(14)ϪC(15) 118.7(4)
C(15)ϪP(2)ϪRh(1)
95.12(4)
84.76(4)
113.4(3)
P(1)ϪRh(1)ϪCl(1)
C(13)ϪP(1)ϪRh(1)
C(14)ϪN(13)ϪC(13) 114.4(4)
C(14)ϪC(15)ϪP(2) 117.7(4)
89.50(4)
115.8(2)
addition,
we
have
clearly
demonstrated
that
Ph2PCH2NHC6H4PPh2 has the potential to ligate in a vari-
ety of bonding modes. The different steric properties or ba-
120.5(2)
1642
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646

The New Unsymmetrical Ligand Ph2PCH2NHC6H4PPh2
FULL PAPER
vacuo to give a viscous oil which was taken up in dichloromethane
(20 cm3) and dried over magnesium sulfate. The drying agent was
removed by filtration and the filtrate was evaporated to dryness.
Addition of diethyl ether to the residue precipitated the product.
The product was collected by suction filtration and dried in vacuo.
Yield: 0.275 g (73%). C31H27NO2P2 (507.5): calcd. C 73.37, H 5.36,
N 2.76; found C 71.01, H 5.29, N 2.74. 31P{1H} NMR (CDCl3):
sicities of the two phosphorus centres can be exploited to
obtain mononuclear complexes where Ph2PCH2-
NHC6H4PPh2 is monodentate (via the Ph2PCH2 moiety) or
chelating, and this latter bonding mode can also be induced
by the use of a halide abstracting agent such as AgI.
Binuclear complexes where Ph2PCH2NHC6H4PPh2 ad-
opts a bidentate bridging coordination mode are also read-
ily accessible. The compounds described represent rare ex-
amples of either complexes containing PCNC2P pendant
1
δ ϭ 28.58 (s, PX), 36.38 (s, PA). H NMR (CDCl3): δ ϭ 4.04 (dd,
3JNH,CH ϭ 6, 2JP,CH ϭ 9 Hz, 2 H, CH2), 6.59Ϫ6.53 (m, 1 H, ArH),
6.78Ϫ6.70 (m, 2 H, ArH), 7.68Ϫ7.26 (m, 22 H, NH ϩ ArH). IR
ligands or MPCNC2P metallacycles. Further studies are (KBr disc): νNH ϭ 3315m cmϪ1, νPϭO ϭ 1179vs, 1167vs, 1118vs
cmϪ1. FAB: m/z ϭ 508 [M ϩ H]ϩ, 530 [M ϩ Na]ϩ.
currently in progress into the synthesis of heterobimetallic
complexes
of
late
transition
metals
of
Ph2P(S)CH2NHC6H4P(S)Ph2 (3): Compound
1
(0.582 g,
Ph2PCH2NHC6H4PPh2 and the coordination properties of
its dichalcogen derivatives Ph2P(O)CH2NHC6H4P(O)Ph2
and Ph2P(S)CH2NHC6H4P(S)Ph2.
1.224 mmol) and elemental sulfur (0.079 g, 2.47 mmol) were stirred
in THF (20 cm3). A white solid began to precipitate in 10 minutes.
Stirring was continued overnight and the product was collected by
suction filtration, washed with diethyl ether (3 ϫ 1 cm3) and dried
in vacuo. Yield: 0.519 g (78.6%). C31H27NS2P2 (539.6): calcd. C
69.00, H 5.04, N 2.60; found C 69.09, H 4.94, N 2.68. 31P{1H}
NMR (CD2Cl2): δ ϭ 38.46 (s, PX), 39.35(s, PA). 1H NMR
Experimental Section
3
2
(CD2Cl2): δ ϭ 4.12 (dd, JNH,CH ϭ 5, JP,CH ϭ 7 Hz, 2 H, CH2),
General: All solvents and reagents were purchased from Aldrich
and Lancaster. Dichloromethane was heated to reflux over pow-
dered calcium hydride and distilled under nitrogen. Diethyl ether
and tetrahydrofuran were purified by reflux over sodium/benzo-
phenone and distillation under nitrogen. Ligand preparations were
performed under an oxygen-free nitrogen atmosphere using stand-
ard Schlenk techniques. Coordination reactions and workup were
performed in dry solvents. 2-(Diphenylphosphanyl)aniline,[16] di-
phenylphosphanylmethanol,[27] [MX2(cod)] (M ϭ Pt, X ϭ Cl or
Me; M ϭ Pd, X ϭ Cl, Br; cod ϭ cycloocta-1,5-diene),[28Ϫ30] [Mo(-
CO)4(pip)2] (pip ϭ piperidine),[31] [AuCl(tht)] (tht ϭ tetrahydrothi-
3
3
6.75Ϫ6.33 (m, 3 H, ArH), 7.03 (br. q, JNH,CH ϭ JNH,CP ϭ 5 Hz,
1 H, NH), 7.67Ϫ7.27 (m, 21 H, ArH). IR (KBr disc): νNH ϭ 3287m
cmϪ1. FAB: m/z ϭ 540 [M ϩ H]ϩ, 562 [M ϩ Na]ϩ.
[PdCl2(Ph2PC6H4NHCH2PPh2-PX,PA)] (4): [PdCl2(cod)] (109 mg,
383 µmol) was added to a solution of Ph2PC6H4NHCH2PPh2 (1;
183 mg, 385 µmol) in CH2Cl2 (20 cm3). The reaction mixture was
stirred for 25 min and then concentrated in vacuo to about 1 cm3
whereupon diethyl ether (10 cm3) was added to precipitate the
product as an orange powder. Yield: 244 mg (98.0%).
C31H27Cl2NP2Pd: calcd. C 57.12, H 4.17, N 2.15; found C 56.51,
ophene),[32] [{MCl(µ-Cl)(η5-C5Me5)}2] (M
ϭ
Rh, Ir),[33] and
H 3.77, N 2.18. 31P{H} NMR ([D6]DMSO): δ ϭ 22.98 (s, PA),
[{RuCl(µ-Cl)(η3:η3-C10H16)}2][34] were prepared using literature
42.72 (s, PX). 1H NMR ([D6]DMSO): δ ϭ 3.96 (t, JP,CH
ϭ
2
procedures.
3
3JNH,CH ϭ 3 Hz, 2 H, CH2), 5.53 (br. dt, JNH,PC ϭ 10 Hz, 1 H,
NH), 6.12Ϫ6.07 (m, 1 H, ArH), 6.28 (m, 1 H, ArH), 6.85Ϫ6.80
(m, 1 H, ArH), 7.23Ϫ7.19 (m, 1 H, ArH), 7.56Ϫ7.35 (m, 20 H,
ArH). IR (KBr disc): νNH ϭ 3253s cmϪ1, νPd-Cl ϭ 312m, 293w
cmϪ1. FAB: m/z ϭ 616 [M Ϫ Cl]ϩ, 580 [M Ϫ 2Cl]ϩ, 674 [M ϩ Na]ϩ.
Infrared spectra were recorded (KBr discs) on a PerkinϪElmer sys-
tem 2000 spectrometer, and 1H NMR spectra (300 MHz) on a
Varian Gemini 2000 spectrometer, 31P{1H} NMR spectra at
101.3 MHz with δ referenced to external 85% H3PO4. Microana-
lysis were performed by the University Service within this Depart-
ment and fast atom bombardment (FAB) or chemical ionization
(CI) mass spectra by the Swansea Mass Spectrometer Service. Pre-
cious metal salts were provided on loan by Johnson Matthey plc.
[PdBr2(Ph2PC6H4NHCH2PPh2-PX,PA)] (5): [PdBr2(cod)] (77 mg,
206 µmol) was added to a solution of Ph2PC6H4NHCH2PPh2 (1;
100 mg, 210 µmol) in CH2Cl2 (5 cm3) and the reaction mixture was
stirred for 30 min. The orange suspension of [PdBr2(cod)] dissolved
immediately and a yellow solid product precipitated gradually. This
precipitate was collected by suction filtration, washed with petro-
leum ether (60Ϫ80, 3 ϫ 1 cm3) and diethyl ether (3 ϫ 1 cm3), yield:
196 mg (68%). C31H27Br2NP2Pd (741.7): calcd. C 50.27, H 3.67, N
1.89; found C 50.11, H 3.89, N 1.86. 31P{1H} NMR ([D6]DMSO):
2-Ph2PC6H4NHCH2PPh2 (1): Ph2PCH2OH (3.00 g, 13.87 mmol)
was added to a solution of 2-(diphenylphosphanyl)aniline (3.84 g,
13.85 mmol) in toluene (150 cm3). The reaction mixture was stirred
at 90Ϫ95 °C for 20 h. The solvent was removed in vacuo and the
sticky residue was dissolved in 20 cm3 of Et2O. Degassed absolute
ethanol (100 cm3) was then added to the ether solution and the
mixture was concentrated in vacuo until a white solid began to
precipitate. Storage in the fridge overnight and filtration gave the
product as a white solid. Yield: 5.46 g (84.4%). C31H27NP2 (475.5):
calcd. C 78.30, H 5.72, N 2.95; found C 77.17, H 5.48, N 2.75.
31P{1H} NMR (CDCl3): δ ϭ Ϫ22.30 (s, PA), Ϫ18.77 (s, PX). 1H
1
δ ϭ 20.55 (s, PA), 41.93 (s, PX). H NMR ([D6]DMSO): δ ϭ 3.92
2
3
3
(br. t, JP,CH ϭ JNH,CH ϭ 3 Hz, 2 H, CH2), 5.44 (br. d, JP,NH
ϭ
25 Hz, 1 H, NH), 6.08 (m, 1 H, ArH), 6.80 (m, 1 H, ArH), 7.16
(m, 1 H, ArH), 7.55Ϫ7.33 (m, 21 H, ArH). IR (KBr disc): νNH
ϭ
3246s cmϪ1, νPd,Cl ϭ 332m, 302vw cmϪ1. FAB: m/z ϭ 663 [M Ϫ
Br]ϩ.
2
3
NMR (CDCl3): δ ϭ 3.83 (t, JP,CH ϭ JCH,NH ϭ 5 Hz, 2 H, CH2),
[PtCl2(Ph2PC6H4NHCH2PPh2-PX,PA)] (6): This colourless com-
plex was prepared in the same manner as compound 4 using
Ph2PC6H4NHCH2PPh2 (1; 80 mg, 168 µmol) in CH2Cl2 (20 cm3)
and [PtCl2(cod)] (62 mg, 168 µmol). Yield: 120 mg (96.0%).
4.97 (br. s, 1 H, NH), 6.64 (t, 1 H, ArH), 6.80 (m, 2 H, ArH),
7.40Ϫ7.20 (m, 21 H, ArH). IR (KBr disc): νNH ϭ 3345m cmϪ1
CI-MS: m/z ϭ 476 [M ϩ H]ϩ.
.
Ph2P(O)CH2NHC6H4P(O)Ph2 (2): Aqueous hydrogen peroxide C31H27Cl2NP2Pt (741.5): calcd. C 50.21, H 3.67, N 1.89; found C
(30% w/w, 0.17 cm3, 1.5 mmol) was added dropwise to a solution 51.42, H 3.70, N 1.75. 31P{1H} NMR (CDCl3): δ ϭ 1.80 (d,
of 1 (0.355 g, 0.75 mmol) in THF (20 cm3) and the mixture was 1JPt,P ϭ 3573 Hz, PA), 20.25 (d, 1JPt,P ϭ 3647 Hz; 2JP ,P ϭ 18 Hz,
A
X
A
stirred for 1.5 hours at 0Ϫ5 °C. The solvent was then removed in
PX). 1H NMR (CD2Cl2): δ ϭ 3.55 (dt, 3JNH,CP ϭ 16 Hz, X1 H, NH),
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646
1643

Q. Zhang, S. M. Aucott, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
3
2
3
3.96 (dd, JNH,CH ϭ 6, JP,CH ϭ 3, JPt,CH ϭ 36 Hz, 2 H, CH2), C41H42Cl2NP2Rh (784.5): calcd. C 62.77, H 5.40, N 1.79; found C
6.29Ϫ6.25 (m, 1 H, ArH), 6.78Ϫ6.72 (m, 1 H, ArH), 7.09Ϫ7.06
62.72, H 5.38, N 1.84. 31P{1H} NMR (CD2Cl2): δ ϭ Ϫ22.84 (s,
1
(m, 1 H, ArH), 7.53Ϫ7.27 (m, 17 H, ArH), 7.74Ϫ7.66 (m, 4 H, PA), 32.74 (d, JRh,P ϭ 141 Hz, PX). 1H NMR (CD2Cl2): δ ϭ 1.33
X
4
3
ArH). IR (KBr disc): νNH ϭ 3265m cmϪ1, νPtϪCl ϭ 316m, 293m (d, JP...CH ϭ 3 Hz, 15 H, CH3), 4.66 (d, JNH,CH ϭ 7 Hz, 2 H,
3
3
2
cmϪ1. FAB: m/z ϭ 741 [M]ϩ, 705 [M Ϫ Cl]ϩ, 764 [M ϩ Na]ϩ.
CH2), 4.97 (br. q, JNH,CH ϭ JPC,NH ϭ 7 Hz, 1 H, NH; no JP,CH
observed), 6.30 (m, 1 H, ArH), 6.40 (m, 1 H, ArH), 6.60 (m, 1 H,
ArH), 6.85 (m, 1 H, ArH), 7.77Ϫ7.04 (m, 20 H, ArH),. IR (KBr
disc): νNH ϭ 3326w cmϪ1. FAB: m/z ϭ 748 [M Ϫ Cl]ϩ, 713 [M
Ϫ 2Cl]ϩ.
[PtMe2(Ph2PC6H4NHCH2PPh2-PX,PA)] (7): [PtMe2(cod)] (50 mg,
149 µmol) was added to a solution of Ph2PC6H4NHCH2PPh2 (1;
71 mg, 149 µmol) in CH2Cl2 (5 cm3). The reaction mixture was
stirred for 30 min and then concentrated in vacuo to about 0.5 cm3
and diethyl ether (1 cm3) and petroleum ether (3 cm3, 60Ϫ80) were
added to precipitate the product as an off-white powder. Yield:
[IrCl2(η5-C5Me5)(Ph2PCH2NHC6H4PPh2-PX)] (11) and [IrCl(η5-
C5Me5)(Ph2PCH2NHC6H4PPh2-PX, PA)]Cl (12): [{IrCl(µ-Cl)(η5-
85 mg (82.0%). C33H33NP2Pt (700.7): calcd. C 56.57, H 4.75, N C5Me5)}2] (70 mg, 88 µmol) was added to
2.00; found C 55.68, H 4.49, N 1.93. 31P{1H} NMR (CDCl3): δ ϭ Ph2PC6H4NHCH2PPh2 (1; 84 mg, 176 µmol) in THF (5 cm3). The
11.91 (d, JPt,P ϭ 1720 Hz, PA), 30.73 (d, JPt,P ϭ 1853 Hz; mixture was stirred for 1.5 h and the solvent was removed in vacuo.
a solution of
1
1
A
X
1
3
3JP ,P ϭ 12 Hz, PX). H NMR (CDCl3): δ ϭ 0.34 (dd, JPЈ,CH
ϭ
The yellow solid residue was dissolved in CH2Cl2 (0.5 cm3) fol-
A
3
X
7, JP,CH ϭ 9, JPtCHЈ ϭ 69 Hz, 3 H, CH3), 0.60 (dd, JP,CH ϭ 7, lowed by addition of acetone (0.5 cm3). Storage of this solution at
2
3
3JPЈCH ϭ 9, JPt,CH ϭ 70 Hz, 3 H, CH3), 3.99 (m, JP,CH ϭ 9 Hz,
3 H, CH2 ϩ NH), 6.23 (m, 1 H, ArH), 6.55 (m, 1 H, ArH), 6.80 orange crystals of 11. The crystals were collected by suction filtra-
(m, 1 H, ArH), 6.93 (t, 1 H, ArH), 7.66Ϫ7.20 (m, 20 H, ArH). IR
tion and washed with acetone (0.5 cm3). Addition of Et2O (2.0 cm3)
room temperature overnight led to the formation of well-shaped
2
2
(KBr disc): νNH ϭ 3337m cmϪ1. FAB: m/z ϭ 700 [M]ϩ, 685 [M Ϫ to the filtrate caused the precipitation of 12 as an orange powder.
CH3]ϩ, 670 [M Ϫ 2CH3]ϩ.
11: Yield: 30 mg (19.5%). C41H42Cl2IrNP2 (873.9): calcd. C 56.35,
H 4.84, N 1.60; found C 56.52, H 4.78, N 1.54. 31P{1H} NMR
(CD2Cl2): δ ϭ Ϫ22.80 (s, PA), 0.10 (s, PX). 1H NMR (CD2Cl2):
[Mo(CO)4(Ph2PC6H4NHCH2PPh2-PX,PA)] (8): [Mo(CO)4(pip)2]
(119 mg, 315 µmol) was added to
a
solution of
4
δ ϭ 1.33 (d, JP...CH ϭ 3 Hz, 15 H, CH3), 4.66 (d, 2 H, CH2; no
Ph2PC6H4NHCH2PPh2 (1; 150 mg, 315 µmol) in CH2Cl2 (25 cm3).
The reaction mixture was stirred at reflux for 3 h and then filtered
through Celite. MeOH (10 cm3) was added to the filtrate, which
was then concentrated under vacuum until trace amounts of solid
appeared. The solution was stored in a fridge overnight. Filtration,
washing with cold MeOH (0.5 cm3) and Et2O (3 ϫ 0.5 cm3) gave
the product as a grey solid. Yield: 105 mg (53%). C35H27MoNO4P2
(683.5): calcd. C 61.50, H 3.98, N 2.05; found C 61.15, H 3.86, N
2.14. 31P{1H} NMR (CD2Cl2): δ ϭ 28.31 (d, PA), 41.43 (d,
3JP ,P ϭ 25 Hz, PX). 1H NMR (CD2Cl2): δ ϭ 4.04 (br. s, 2 H,
3
2JPCH observed), 4.91 (q, JNH,CH
ϭ
3JPCNH ϭ 7 Hz, 1 H, NH),
6.34 (m, 1 H, ArH), 6.42 (m, 1 H, ArH), 6.61 (m, 1 H, ArH),
7.71Ϫ6.91 (m, 21 H, ArH). IR (KBr disc): νNH ϭ 3328w cmϪ1
FAB: m/z ϭ 838 [M Ϫ Cl]ϩ, 803 [M Ϫ 2Cl]ϩ.
.
12: Yield: 29 mg (19%). C41H42Cl2IrNP2 (873.9): calcd. C 56.35, H
4.84, N 1.60; found C 48.67, H 4.33, N 1.08. 31P{1H} NMR
(CD2Cl2): δ ϭ Ϫ0.32 (s), 0.48 (s). IR (KBr disc): νNH ϭ 3283w
cmϪ1. FAB: m/z ϭ 838 [M Ϫ Cl]ϩ, 803 [M Ϫ 2Cl]ϩ.
[RuCl(η3:η3-C10H16)(Ph2PCH2NHC6H4PPh2-PX,PA)][ClO4] (13):
A
B
CH2), 6.63Ϫ6.56 (m, 1 H, ArH), 6.78Ϫ6.71 (m, 2 H, ArH), [{RuCl(µ-Cl)(η3:η3-C10H16)}2] (64 mg, 103 µmol) was added to a
7.55Ϫ7.26 (m, 22 H, ArH ϩ NH). IR (KBr disc): νNH ϭ 3389w
solution of Ph2PC6H4NHCH2PPh2 (1; 99 mg, 208 µmol) in THF
cmϪ1, νCϵO ϭ 2013vs, 1914vs, 1878vs, 1892vs cmϪ1. FAB: m/z ϭ (5 cm3). The mixture was stirred for 1.5 h and then AgClO4 (43 mg,
684 [M]ϩ, 656 [M Ϫ CO]ϩ, 628 [M Ϫ 2CO]ϩ, 600 [M Ϫ 3CO]ϩ,
572 [M Ϫ 4CO]ϩ.
207 µmol) was added. Stirring was continued overnight and the
precipitated AgCl was removed by filtration through Celite. The
dark filtrate was concentrated in vacuo to ca. 0.5 cm3. Addition of
Et2O (5 cm3), filtration and washing with Et2O (3 ϫ 1 cm3) gave the
product as a black solid. Yield: 162 mg (92%). C41H43Cl2NO4P2Ru
(847.7): calcd. C 58.09, H 5.11, N 1.65; found C 56.88, H 4.85, N
[RuCl2(η3:η3-C10H16)(Ph2PCH2NHC6H4PPh2-PX)] (9): [{RuCl(µ-
Cl)(η3:η3-C10H16)}2] (80 mg, 130 µmol) was added to a solution of
Ph2PC6H4NHCH2PPh2 (1; 124 mg, 261 µmol) in THF (5 cm3). The
mixture was stirred for 1.5 h and then concentrated to ca. 0.5 cm3.
Addition of Et2O (2 cm3), filtration and washing with Et2O (3 ϫ
1 cm3) gave the product as a pale brown solid. Yield: 179 mg (88%).
C41H43Cl2NP2Ru (783.7): calcd. C 62.84, H 5.53, N 1.79; found C
62.61, H 5.72, N 1.71. 31P{H} NMR (CDCl3): δ ϭ Ϫ22.51(s, PA),
16.80 (s, PX). 1H NMR (CD2Cl2): δ ϭ 2.15 (s, 6 H, CH3), 2.65 (m,
2 H, CH2), 3.18 (m, 2 H, CH2), 3.43 (d, 2 H, CH), 4.03 (d, 2
H,CH), 4.59 (dd, 3JNH,CH ϭ 6, 2JP,CH ϭ 2 Hz, 2 H, CH2), 4.95 (m,
1
2.05. 31P{1H} NMR (CDCl3): δ ϭ 21.86 (s, PA), 36.89 (s, PX). H
NMR (CDCl3): δ ϭ 2.14 (s, 6 H, CH3), 2.64 (br. m, 2 H, CH2),
3.22 (d, 2 H, CH), 3.43 (m, 2 H, CH2), 4.12 (d, 2 H, CH), 4.67
2
3
3
(ddd, JP,CH ϭ 52, JP,CH ϭ 15, JCH,NH ϭ 6 Hz, 2 H, CH2), 5.02
(br. s, 1 H, NH), 5.13 (br. m, 2 H, CH), 6.42 (m, 2 H, ArH), 6.63
(m, 1 H, ArH), 7.75Ϫ7.05 (m, 21 H, ArH). IR (KBr disc): νNH
ϭ
3272w cmϪ1, νClO ϭ 1099 vs cmϪ1. FAB: m/z ϭ 748 [M Ϫ ClO4]ϩ.
Ϫ
4
1 H, NH), 5.13 (br. m, 2 H, CH), 6.73Ϫ6.54 (m, 3 H, ArH), [RhCl(η5-C5Me5)(Ph2PCH2NHC6H4PPh2-PX,PA)][ClO4] (14): This
7.38Ϫ6.99 (m, 17 H, ArH), 7.76Ϫ7.59 (m, 4 H, ArH). IR (KBr orange product was prepared in the same way as the ruthenium
disc): νNH ϭ 3314w cmϪ1. FAB: m/z ϭ 784 [M]ϩ, 748 [M Ϫ Cl]ϩ, compound 13 from [{RhCl(µ-Cl)(η5-C5Me5)}2] (25 mg, 40 µmol),
713 [M Ϫ 2Cl]ϩ.
Ph2PC6H4NHCH2PPh2 (1; 39 mg, 82 µmol) and AgClO4 (17 mg,
82 µmol). Yield: 63 mg (93%). Red crystals suitable for X-ray ana-
lysis were obtained by layering THF and petroleum ether (60Ϫ80)
[RhCl2(η5-C5Me5)(Ph2PCH2NHC6H4PPh2-PX)] (10): [{RhCl(µ-
Cl)(η5-C5Me5)}2] (68 mg, 110 µmol) was suspended in THF (4 cm3)
and Ph2PC6H4NHCH2PPh2 (1; 105 mg, 220 µmol) was added to
the stirred suspension as a solid in one portion. The suspension
dissolved and after 15 minutes stirring, an orange solid deposited
from the deep red solution. After stirring for a total of 2 h the
orange solid was collected by suction filtration, washed with diethyl
ether (3 ϫ 1 cm3) and dried in vacuo. Yield: 145 mg (87%).
on
a
dichloromethane solution of 14 for four days.
C41H42Cl2NO4P2Rh (848.5): calcd. C 58.03, H 4.99, N 1.65; found
C 57.49, H 4.87, N 1.52. IR (KBr disc): νNH ϭ 3332m cmϪ1
,
νClO ϭ 1095vs cmϪ1. FAB: m/z ϭ 748 [M Ϫ ClO4]ϩ.
Ϫ
4
[Ph2P{AuCl}CH2NHC6H4{AuCl}PPh2] (15): [AuCl(tht)] (135 mg,
420 µmol) was added to a solution of Ph2PC6H4NHCH2PPh2 (1;
1644
Eur. J. Inorg. Chem. 2002, 1635Ϫ1646

The New Unsymmetrical Ligand Ph2PCH2NHC6H4PPh2
FULL PAPER
Table 8. Details of the X-ray data collections and refinements for compounds 2, 3, 8, 9, 11 and 14
2·0.5H2O
3
8
9
11
14
Empirical formula
Crystal colour, habit
Crystal dimensions/mm
Crystal system
C31H27NO2.50P2 C31H27NP2S2
clear, prism clear, prism
0.21 ϫ 0.1 ϫ 0.1 0.1 ϫ 0.1 ϫ 0.08 0.16 ϫ 0.13 ϫ 0.13 0.12 ϫ 0.1 ϫ 0.06 0.15 ϫ 0.1 ϫ 0.1 0.18 ϫ 0.12 ϫ 0.1
C35H27MoNO4P2 C41H43Cl2NP2Ru C41H42Cl2IrNP2 C41.25H42.50Cl2.50NO4P2Rh
clear, prism purple, prism Orange, block Red, prism
Monoclinic
C2/c
Triclinic
P1
Monoclinic
P21/c
Triclinic
P1
Monoclinic
P21/c
Triclinic
P1
¯
¯
¯
Space group
˚
a (A)
26.754(2)
9.0619(6)
25.046(2)
90
119.409(2)
90
9.6227(3)
12.3446(4)
13.2192(3)
108.7150(10)
110.4580(10)
93.9340(10)
1364.24 (7)
2
14.3816(3)
9.9445(2)
22.5402(4)
90
103.5250(10)
90
10.676(2)
13.333(3)
13.646(3)
76.527(5)
74.373(4)
79.345(5)
1803.6(6)
2
18.5451 (2)
9.1119(1)
22.3655(1)
90
92.5500(10)
90
12.3348(5)
12.3577(5)
14.1891(6)
77.3270(10)
78.15
81.8740(10)
2054.6(2)
2
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
3
˚
U (A )
5289.8(7)
8
3134.25(11)
4
3775.60(6)
4
Z
M
516.48
1.297
0.196
2168
539.60
1.314
0.334
564
683.46
1.448
0.560
1392
783.67
1.443
0.702
808
873.80
1.537
3.792
1744
724.43
1.406
0.697
893
Dc (g cmϪ3
)
µ (mmϪ1
F(000)
)
Measured reflections
12820
6916
13208
9120
15695
14534
Independent reflections (Rint
Final R1, ωR2[I Ͼ 2σ(I)]
)
3756 (0.0806)
0.0566, 0.1316
3882 (0.0176)
0.0412, 0.0993
0.250, Ϫ0.230
4485 (0.0256)
0.0236, 0.0558
0.222, Ϫ0.171
5066 (0.1443)
0.0842, 0.1770
0.670, Ϫ0.882
5376 (0.0367)
0.0293, 0.0650
0.200, Ϫ0.254
5860 (0.0280)
0.0434, 0.1127
0.731, Ϫ0.528
Largest difference peak hole (eAϪ3) 0.337, Ϫ0.448
˚
100 mg, 210 µmol) in CH2Cl2 (10 cm3). The mixture was stirred
Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ44-1223/336-
for 30 minutes and then filtered through Celite. The filtrate was 033; E-mail: deposit@ccdc.cam.ac.uk].
concentrated to ca. 0.5 cm3. Addition of 60Ϫ80 petroleum ether
(10 cm3), filtration and washing with Et2O (3 ϫ 1 cm3) gave the
product as a white solid. Yield: 176 mg (90%). C31H27Au2Cl2NP2
Acknowledgments
We wish to thank the JREI for equipment grants and Johnson Mat-
they plc for the loan of precious metals. Qingzhi Zhang is indebted
to St Andrews University for financial support.
(940.3): calcd. C 39.60, H 2.89, N 1.49; found C 39.91, H 2.91, N
1
1.48. 31P{1H} NMR (CDCl3): δ ϭ 18.64 (s, PA), 24.95 (s, PX). H
2
NMR (CDCl3): δ ϭ 4.34 (dd, JP,CH ϭ 3 Hz, 2 H, CH2), 4.94 (m,
3JNH,CH ϭ 6, 3JPCNH ϭ 4JPCCNH ϭ 3 Hz, 1 H, NH), 6.61 (m, 1 H,
ArH), 6.79 (m, 1 H, ArH), 6.99 (m, 1 H, ArH), 7.58Ϫ7.40 (m, 21
H, ArH). IR (KBr disc): νNH ϭ 3309m cmϪ1, νAu-Cl ϭ 329m cmϪ1
FAB: m/z ϭ 904 [M Ϫ Cl]ϩ.
.
[1]
R. J. Puddephatt, Chem. Soc. Rev. 1983, 99Ϫ127.
[2]
I. Haiduc, I. S. Dumitrescu, Coord. Chem. Rev. 1986, 69,
127Ϫ258.
[{RhCl2(η5-C5Me5)}2(Ph2PCH2NHC6H4PPh2)] (16): This com-
pound was prepared in the same way as compound 10 from a 1:1
molar ratio of [{RhCl(µ-Cl)(η5-C5Me5)}2] (93 mg, 150 µmol) and
Ph2PC6H4NHCH2PPh2 (1; 73 mg, 151 µmol). Yield: 148 mg (90%).
C51H57Cl4NP2Rh (1093.6): calcd. C 54.33, H 5.25, N 1.28; found
C 56.01, H 4.66, N 1.16. 31P{1H} NMR (CDCl3): δ ϭ 27.79 (d,
[3]
B. Chaudret, B. Delavaus, R. Poilblanc, Coord. Chem. Rev.
1988, 86, 191Ϫ243.
E. Drent, J. A. M. van-Broekhoven, M. J. Doyle, J. Organomet.
[4]
Chem. 1991, 417, 235Ϫ251.
C. P. C. M. Dekker, C. J. Elsevier, K. Vrieze, P. W. N. M. van
[5]
Leeuwen, Organometallics 1992, 11, 1598Ϫ1603.
E. M. Barranco, M. C. Gimeno, P. G. Jones, A. Laguna, M.
[6]
1
1
1JRh,P ϭ 144 Hz, PA), 32.44 (d, JRh,P ϭ 138 Hz, PX). H NMR
(CDCAl3): δ ϭ 1.23 (d, 4JP,CH ϭ 3 Hz, 15 H, CH3), 1.27 (d, 4JP,CH ϭ
X
D. Villacampa, Inorg. Chem. 1999, 38, 702Ϫ706.
B. Buriez, I. D. Burns, A. F. Hill, A. J. P. White, D. J. Williams,
[7]
3
2
3 Hz, 15 H, CH3), 4.90 (dd, JNH,CH ϭ 5, JP,CH ϭ 16 Hz, 2 H,
CH2), 5.33 (br. s, 1 H, NH), 5.78 (m, 1 H, ArH), 6.28 (m, 1 H,
ArH), 6.52 (m, 1 H, ArH), 6.70 (m, 1 H, ArH), 7.89Ϫ6.90 (m, 20
H, ArH). IR (KBr disc): νNH ϭ 3280m cmϪ1. FAB: m/z ϭ 1056
[M Ϫ Cl]ϩ.
J. D. E. T. Wilton-Ely, Organometallics 1999, 18, 1504Ϫ1516.
[8]
B. S. Williams, K. I. Goldberg, J. Am. Chem. Soc. 2001, 123,
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