P- versus P,O- coordination in complexes of N-(diphenylphosphino)arylamide ligands ArC(O)NHPPh2 (Ar = 3-pyridyl, phenyl). X-ray crystal structures of [RhCl2(η5-C5Me5) L2] and [NiCl(EtOH)L<s

Article abstract of DOI:10.1016/S0277-5387(01)00734-3

The N-(diphenylphosphino)arylamide ligands 3-NC₅H₄CONHPPh₂ (L¹) and C₆H₅CONHPPh₂ (L²) function as monodentate p-donors in the complexes [RhCl₂(η⁵

Full text of DOI:10.1016/S0277-5387(01)00734-3

Polyhedron 20 (2001) 1803–1808
www.elsevier.com/locate/poly
P- versus P,O- coordination in complexes of
N-(diphenylphosphino)arylamide ligands
ArC(O)NHPPh2 (Ar=3-pyridyl, phenyl).
X-ray crystal structures of [RhCl2(h5-C5Me5)L2]
and [NiCl(EtOH)L22 ]·Cl·[NiCl2L22 ] (L2=C6H5CONHPPh2)
Pravat Bhattacharyya, Tuan Q. Ly, Alexandra M.Z. Slawin, J. Derek Woollins *
Department of Chemistry, Uni6ersity of St Andrews, St Andrews, Fife KY16 9ST, UK
Received 16 June 2000; accepted 7 December 2000
Abstract
The N-(diphenylphosphino)arylamide ligands 3-NC5H4CONHPPh2 (L1) and C6H5CONHPPh2 (L2) function as monodentate
p-donors in the complexes [RhCl2(h5-C5Me5)L], [RuCl2(h6-p-cymene)L] and cis-[PtCl2L2], as exemplified by the X-ray crystallo-
graphically determined structure of [RhCl2(h5-C5Me5)L2]. For nickel(II), P,O- chelation by L1,2 is exhibited in the bis(bidentate)
complexes [NiCl2L2], as demonstrated by the crystal structure of [NiCl(EtOH)L22 ]·Cl·[NiCl2L22 ]; the five-membered NiꢀOꢀCꢀNꢀP
chelate rings are approximately planar with the phosphorus atoms in the dichloro complex being trans whereas their arrangement
is cis in the cation. Comparison of this structure with [RhCl2(h5-C5Me5)L2] reveals slight elongation of the CꢁO and PꢀN lengths
upon P,O-chelation of L2. Solvatochromism for the Ni(II)-L2 complex (green in ethanol or acetone, brown in chlorinated solvents)
arises from solvent-dependent hemilability of the amide oxygen atom, although the L1 complex of Ni(II) is exempt from this
behaviour. © 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Phosphinoamide; Heterobidentate; Solvatochromism; Complexes; X-ray
chlorophosphines with primary amines in the presence
of a tertiary amine base, has received widespread atten-
1. Introduction
tion [1–7]. The importance of mono- and bidentate
phosphorus(III) ligands in a multiplicity of homoge-
neous catalytic applications and the enormous diversity
of amines available have fuelled interest in this bur-
geoning area, leading to the rapid establishment of an
extensive library of ligands constructed by PꢀN bond
formation.
In recent years the synthesis and coordination chem-
istry of phosphorus(III) ligands containing PꢀN link-
ages, generally derived by the condensation of
Despite this increasing interest in PꢀN bond forma-
tion as a ligand construction methodology, phospho-
rus(III) functionalised (i.e. containing a PꢀN linkage)
amides and thioamides remain rare [8–12]. While P- or
E- monodentate (E=O or S) and P,E- chelation modes
are available for these compounds, the amide oxygen
(or sulphur) atom is in general reluctant to bind to
transition metal centres. The prominence of ambiden-
tate P,O- donor ligands in catalysis, whose activity
stems from partially labile metal–oxygen bonds [13–
Fig. 1. Structures of L1,2
.
* Corresponding author. Tel.: +44-1334-463861; fax: +44-1334-
463384.
E-mail address: jdw3@st-and.ac.uk (J. Derek Woollins).
0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0277-5387(01)00734-3

1804
P. Bhattacharyya et al. / Polyhedron 20 (2001) 1803–1808
17], suggests that further exploration of phosphi-
noamide ligands is overdue.
the free ligand values (1639, 1654 cm−1 for L1, L2)
whereas for 7, 8 there is a reduction by a similar
amount (1618 and 1604 cm−1); an analogous sensitivity
in w(CO) energies upon coordination of the carbonyl
oxygen has been noted in platinum(II) and palladiu-
m(II) complexes of the N-donor iminophosphorane
ligands Ph3PꢁNC(O)CH2Cl and Ph3PꢁNC(O)-2-NC5H4
We have reported previously that Ph2P(O)NHPPh2 is
adept at P-monodentate and P,O- bidentate coordina-
tion modes in both its neutral form and as the monoan-
ion [Ph2P(O)NPPh2]− at platinum(II), ruthenium(II)
and iridium(III) [1,2,5]. This versatility has prompted us
to investigate the related P,O-hybrids 3-NC5H4-
CONHPPh2 (L1) and C6H5CONHPPh2 (L2) (Fig. 1) as
a new class of heterobidentate ligands which exhibit
both mono- and bidentate behaviour for selected transi-
tion metals.
[20]. The w(NH) vibration in L1,2 (3264 and 3262 cm−1
,
respectively) moves 30–50 cm−1 to lower energy upon
complexation to platinum(II) while conversely there is
an increase by approximately 50 cm−1 in this band for
[RhCl2(h5-C5Me5)L] and [RuCl2(h6-p-cymene)L]. The
w(NH) bands of 7, 8 are obscured by the w(OH) absorp-
tion from the coordinated ethanol molecule.
1
2. Results and discussion
In the 31P{1H} NMR spectra of 5, 6 the J(PtꢀP)
coupling constants (3849, 3876 Hz) confirm the cis
geometry of L ligands, their magnitude being substan-
tially larger than for cis-[PtCl2(PPh3)2] (3677 Hz), sug-
gesting a greater electronegativity for an N-arylamido
group compared with C6H5. In 1, 2 the 1J(RhꢀP)
coupling constants (149 and 145 Hz, respectively) are
comparable with the values of 145 and 147 Hz for
L=PPh3 and Ph2P(O)NHPPh2ꢀP [2,21]. While no ap-
preciable coordination shift is noted for the phosphorus
atom in the platinum(II) complexes 5, 6 the lP values
for L1,2 (26.0 and 25.0 ppm) move by 30 ppm to high
frequency upon complexation to rhodium(III) and
ruthenium(II). The nickel(II) complexes 7, 8 are para-
magnetic in all solvents, precluding NMR measure-
ments. As found for L1,2 there is little variation in lP
Cleavage of [{RhCl(m-Cl)(h5-C5Me5)}2] or [{RuCl(m-
Cl)(h6-p-cymene)}2] with
2
equiv. of L1,2 in
dichloromethane gives [RhCl2(h5-C5Me5)L] (L=L1
1
or L2 2) and [RuCl2(h6-p-cymene)L] (L=L1 (3) or L2
(4)), respectively, while the treatment of [PtCl2-
(MeCN)2] with 2 equiv. of L1,2 leads to bis(phosphine)
complexes cis-[PtCl2L2] (L=L1 (5) or L2 (6)). In the
ruthenium(II), rhodium(III) and platinum(II) com-
plexes L1,2 are coordinated to the metal centre through
the phosphorus(III) atom only, the non-coordination of
the oxygen atom is analogous to Ph2P(O)NHPPh2
[1,2,5] and Ph2PCH2C(O)R [15,18,19], which are P-
monodentate at late transition metals. This assertion is
further supported by the crystal structure of [RhCl2(h5-
C5Me5)L2] (2) (vide infra) in which the carbonyl group
of L2 is pendant. The complexes 1–6 are air- and
moisture- stable solids soluble in chlorinated solvents,
acetone and THF.
1
with the N-aryl substituent in 1–6. In the H NMR
4
spectra of 1, 2 the J(PꢀCH3) coupling constant of 31P
to the C5Me5 ring protons is 4 Hz.
Attempts to prepare nickel(II) complexes of L1,2 in
ethanol–dichloromethane are complicated by partial
solvolysis of one geometric isomer of [NiCl2L2]. X-ray
crystallographic analysis of the product from the NiCl2-
L2 system (vide infra) shows it to be [NiCl(E-
tOH)L22 ]·Cl·[NiCl2L22 ] (8). A similar fate undoubtedly
befalls the corresponding L1 complex 7. Notably 8 is
solvatochromic, being green in ethanol and acetone
whereas solutions in chlorinated solvents are brown; the
green colour is restored upon removal of the solvent,
suggesting a facile solvent-dependent interconversion
between P,O-bidentate (green) and P-monodentate
(brown) forms. However the sparingly soluble 7 retains
its turquoise colour in all solvents, indicating that the
donor properties of the carbonyl oxygen in L1,2 are
modulated to some extent by the aryl group.
2.1. Single crystal X-ray diffraction studies
The molecular structure of [RhCl2(h5-C5Me5)L2] (2)
(Fig. 2) displays a piano-stool geometry with an h5-
bound pentamethylcyclopentadienyl ring and two chlo-
ride ligands Cl(1) and Cl(2), with L2 bound through
P(1) completing the coordination sphere at Rh(1). The
C(13)ꢀO(13) vector is directed away from Rh(1) and is
uninvolved in hydrogen-bonding interactions with adja-
cent molecules, however there are internal bifurcated
hydrogen bonds between H(1N) and the chloride lig-
,
,
ands [H(1N)···Cl(1) 2.52 A, H(1N)···Cl(2) 2.90 A;
N(1)ꢀH(1N)···Cl(1) 116°, N(1)ꢀH(1N)···Cl(2) 113°]. The
bond lengths within the metal coordination sphere are
,
unexceptional [Rh(1)ꢀP(1) 2.318(2) A, Rh(1)ꢀCl(1)
,
,
2.404(1) A, Rh(1)ꢀCl(2) 2.406(1) A, Rh(1)···C5Me5
,
The complexes 1–8 have been characterised using
NMR, FAB+ mass and IR spectroscopies and by ele-
mental analyses, the most prominent peaks in their
FAB+ mass spectra corresponding to [M+−Cl]. In
their IR spectra, the carbonyl bands for 1–6 (1674–
1686 cm−1) are raised by approximately 40 cm−1 from
(centroid) 1.83 A], the RhꢀP distance comparing fa-
vourably with isostructural complexes [2.254(3)–
,
2.332(3) A] [21,22].
As outlined above, attempts to prepare [NiCl2L22 ] in
ethanol are accompanied by NiꢀCl hydrolysis, noted
during the recrystallisation of [NiCl2L22 ] from ethanol–

P. Bhattacharyya et al. / Polyhedron 20 (2001) 1803–1808
1805
molecules contribute to the poor R factor of 9.8% for
this structure. The complexation of L2 to nickel(II)
generates both cis,trans,cis and cis,cis,cis isomers of
[NiCl2(L2-P,O)2]; the formation of 8a from 8b can be
attributed to the labilising influence of P(2) on the trans
NiꢀCl bond in the cis,cis,cis isomer, promoting dis-
placement of the chloro ligand by an ethanol molecule
to give the cationic complex [NiCl(EtOH)L22 ]Cl (8a).
Both 8a,b show substantial distortion from regular
octahedral geometry, the cis angles are between
77.6(2)–111.84(11)° and 77.6(2)–98.39(11)°, the
OcarbonylꢀNiꢀP angles within the chelate rings being the
smallest [O(13)ꢀNi(1)ꢀP(1) 79.6(2)°, O(33)ꢀNi(1)ꢀP(2)
77.6(2)° in 8a; O(53)ꢀNi(2)ꢀP(3) 77.6(2)°, O(73)ꢀ
Ni(2)ꢀP(4) 78.0(2)° in 8b]. The unequal NiꢀOcarbonyl and
Fig. 2. Molecular structure of [RhCl2(h5-C5Me5)L2] (2) (CꢀH atoms
,
omitted for clarity). Selected bond lengths (A) and angles (°);
,
NiꢀP bond lengths in 8a [Ni(1)ꢀO(33) 2.026(7) A,
Rh(1)ꢀP(1) 2.318(2), Rh(1)ꢀCl(1) 2.404(1), Rh(1)ꢀCl(2) 2.406(1),
P(1)ꢀN(1) 1.696(5), N(1)ꢀC(13) 1.366(7), C(13)ꢀO(13) 1.231(6);
P(1)ꢀRh(1)ꢀCl(1) 87.39(5), P(1)ꢀRh(1)ꢀCl(2) 88.67(5), Cl(1)ꢀ
Rh(1)ꢀCl(2) 89.31(6), N(1)ꢀP(1)ꢀRh(1) 107.8(2), C(13)ꢀN(1)ꢀP(1)
129.1(4), O(13)ꢀC(13)ꢀN(1) 122.7(5).
Table 1
Selected bond lengths (A) and angles (°) for [NiCl(EtOH)L22 ]·
,
Cl·[NiCl2L22 ] (8) (e.s.d.s in parentheses)
[NiCl(EtOH)L2 2].Cl (8a)
Bond lengths
Ni(1)ꢀO(33)
Ni(1)ꢀO(1)
Ni(1)ꢀP(1)
P(1)ꢀN(1)
2.026(7)
2.142(7)
2.376(3)
1.733(9)
1.256(12)
Ni(1)ꢀO(13)
Ni(1)ꢀCl(1)
Ni(1)ꢀP(2)
P(2)ꢀN(2)
2.119(7)
2.308(3)
2.502(3)
1.722(9)
1.244(10)
C(13)ꢀO(13)
C(33)ꢀO(33)
Bond angles
O(33)ꢀNi(1)ꢀO(13) 89.3(3)
O(13)ꢀNi(1)ꢀO(1) 82.0(3)
O(13)ꢀNi(1)ꢀCl(1) 173.9(2)
O(33)ꢀNi(1)ꢀO(1) 82.4(3)
O(33)ꢀNi(1)ꢀCl(1) 96.5(2)
O(1)ꢀNi(1)ꢀCl(1)
O(13)ꢀNi(1)ꢀP(1)
Cl(1)ꢀNi(1)ꢀP(1)
O(13)ꢀNi(1)ꢀP(2)
Cl(1)ꢀNi(1)ꢀP(2)
96.8(2)
O(33)ꢀNi(1)ꢀP(1)
O(1)ꢀNi(1)ꢀP(1)
O(33)ꢀNi(1)ꢀP(2)
O(1)ꢀNi(1)ꢀP(2)
P(1)ꢀNi(1)ꢀP(2)
C(13)ꢀN(1)ꢀP(1)
165.3(2)
86.5(2)
77.6(2)
158.8(2)
111.84(11) N(1)ꢀP(1)ꢀNi(1)
117.7(9)
79.6(2)
94.37(12)
90.7(2)
92.37(11)
98.1(4)
O(13)ꢀC(13)ꢀN(1) 123.3(13)
N(2)ꢀP(2)ꢀNi(1) 95.9(3)
C(33)ꢀO(33)ꢀNi(1) 126.7(7)
C(13)ꢀO(13)ꢀNi(1) 119.7(8)
O(33)ꢀC(33)ꢀN(2) 120.2(10)
C(33)ꢀN(2)ꢀP(2)
118.3(8)
[NiCl2L2 2] (8b)
Bond lengths
Ni(2)ꢀO(73)
Ni(2)ꢀCl(2)
Ni(2)ꢀP(3)
2.097(6) Ni(2)ꢀO(53)
2.112(7)
2.359(3)
2.418(3)
1.742(8)
1.248(9)
2.387(3) Ni(2)ꢀCl(3)
2.387(3) Ni(2)ꢀP(4)
1.708(8) P(4)ꢀN(4)
1.235(11) C(73)ꢀO(73)
P(3)ꢀN(3)
C(53)ꢀO(53)
Bond angles
O(73)ꢀNi(2)ꢀO(53)
O(53)ꢀNi(2)ꢀCl(3)
O(53)ꢀNi(2)ꢀP(3)
O(73)ꢀNi(2)ꢀCl(2)
Cl(3)ꢀNi(2)ꢀCl(2)
O(73)ꢀNi(2)ꢀP(4)
Cl(3)ꢀNi(2)ꢀP(4)
Cl(2)ꢀNi(2)ꢀP(4)
C(53)ꢀN(3)ꢀP(3)
85.2(3)
89.4(2)
77.6(2)
88.9(2)
O(73)ꢀNi(2)ꢀCl(3) 173.5(2)
O(73)ꢀNi(2)ꢀP(3)
Cl(3)ꢀNi(2)ꢀP(3)
85.8(2)
96.69(11)
O(53)ꢀNi(2)ꢀCl(2) 173.1(2)
96.72(12) P(3)ꢀNi(2)ꢀCl(2)
78.0(2) O(53)ꢀNi(2)ꢀP(4)
98.21(11) P(3)ꢀNi(2)ꢀP(4)
93.56(11) N(3)ꢀP(3)ꢀNi(2)
98.39(11)
88.7(2)
159.65(12)
99.7(3)
Fig. 3. Molecular structures of the nickel complexes in [NiCl(E-
tOH)L22 ]·Cl·[NiCl2L22 ] (8) (CꢀH atoms omitted for clarity).
118.1(8)
O(53)ꢀC(53)ꢀN(3) 120.1(12)
N(4)ꢀP(4)ꢀNi(2) 97.7(3)
O(73)ꢀC(73)ꢀN(4) 119.6(10)
diethyl ether. The unit cell contains two distinct species
[NiCl(EtOH)L22 ]Cl and [NiCl2L22 ], hereafter 8a and 8b,
respectively (Fig. 3, Table 1). The co-crystallisation of
8a,b and the inclusion of ethanol and methanol solvate
C(53)ꢀO(53)ꢀNi(2) 124.0(8)
C(73)ꢀN(4)ꢀP(4) 119.1(7)
C(73 ꢀO(73)ꢀNi(2) 124.2(7)
–

1806
P. Bhattacharyya et al. / Polyhedron 20 (2001) 1803–1808
Table 2
conditions. L1,2, [{RhCl(m-Cl)(h5-C5Me5)}2], [{RuCl(m-
Cl)(h6-p-cymene)}2] and [PtCl2(MeCN)2] were prepared
by literature methods [8,23–25], solvents were of
reagent grade. 1H and 31P{1H} NMR spectra (250.1
and 36.2 MHz, CHCl3-d) were recorded on Bruker
AM250 and JEOL FX90Q NMR spectrometers and
referenced to external SiMe4 (l 0) and 85% H3PO4 (l
0), respectively, using the high-frequency positive con-
vention. IR spectra (KBr discs) were recorded on a
Perkin–Elmer System 2000 NIR FT-Raman spectrome-
ter, elemental analyses (PE 2400 CHN elemental analy-
ser) were performed by the University of Lough-
borough Analytical Service, and FAB+ mass spectra
(3-NOBA matrix) by the EPSRC National Mass Spec-
trometry Service Centre, Swansea.
,
Hydrogenꢀbonding distances (A) and angles (°) for [NiCl(E-
tOH)L22]·Cl·[NiCl2L22] (8) (e.s.d.s in parentheses) a
Bond lengths
H(1N)···O(91)
H(2N)···Cl(4)
H(3N)···Cl(4)
H(4N)···Cl(4%)
1.86 H(1O)···O(93)
2.48 H(1O)···O(33)
2.49 H(91O)···Cl(2%)
2.36 H(93O)···Cl(3%)
1.83
2.43
2.24
2.19
Bond angles
N(1)−H(1N)···O(91)
N(2)−H(2N)···Cl(4)
N(3)−H(3N)···Cl(4)
N(4)−H(4N)···Cl(4%)
171
151
176
175
O(1)−H(1O)···O(93)
156
98
162
166
O(1)−H(1O)···O(33)
O(91)−H(91O)···Cl(2%)
O(93)−H(93O)···Cl(3%)
a O(91), O(93) are oxygen atoms from ethanol solvate molecules, %
refers to a symmetry-related atom.
,
,
Ni(1)ꢀO(13) 2.113(7) A; Ni(1)ꢀP(1) 2.376(3) A, Ni(1)ꢀ
4.1. [RhCl2(p5-C5Me5)L]
,
P(2) 2.502(3) A] reflect differences in trans influences
A dichloromethane solution (1 cm3) of L (0.1 mmol)
was added to [{RhCl(m-Cl)(h5-C5Me5)}2] (0.05 mmol)
in dichloromethane (1 cm3) and stirred for 24 h. Va-
pour diffusion of diethyl ether into this solution gave
[RhCl2(h5-C5Me5)L] (L=L1 (1) or L2 (2)) as deep red
crystals. Compound 1 Yield: 80%. Anal. Found: C,
54.7; H, 5.0; N, 4.2. Calc. for C28H30N2OPRhCl2: C,
54.0; H, 4.9; N, 4.5%. 31P NMR: l=63.9(d),
(1J(RhꢀP)=149 Hz). 1H NMR: l=9.08–7.53 (m,
,
compared with 8b [Ni(2)ꢀO(53) 2.112(7) A, Ni(2)ꢀO(73)
,
,
2.097(6) A; Ni(2)ꢀP(3) 2.387(3) A, Ni(2)ꢀP(4) 2.418(3)
,
A]. The five-membered nickelacycles in 8a,b are
essentially planar [mean deviations of Ni(1)ꢀP(1)ꢀ
N(1)ꢀC(13)ꢀO(13) and Ni(1)ꢀP(2)ꢀN(2)ꢀC(33)ꢀO(33)
,
planes of 0.07 and 0.06 A, respectively, in 8a, mean
deviations of Ni(2)ꢀP(3)ꢀN(3)ꢀC(53)ꢀO(53) and
Ni(2)ꢀP(4)ꢀN(4)ꢀC(73)ꢀO(73) planes of 0.03 and 0.05
,
A, respectively, in 8b]. There are only modest increases
4
in CꢁO and PꢀN bond lengths upon O-coordination
14H, aromatic H), 1.44 (d, 15H, J=4 Hz, C5Me5). IR
(cm−1): w(NH) 3264; w(CO) 1683. FAB+ MS: 579,
M+−Cl.
,
,
compared with 2 [PꢀN 1.696(5) A, CꢁO 1.231(6) A in 2,
,
cf. 1.708(8)–1.742(8) and 1.235(11)–1.256(12) A,
respectively, in 8a,b]. There is an extensive array of
hydrogen-bonding interactions involving the Cl(4)
counterion, the amine protons H(1N)–H(4N), the
co-ordinated ethanol molecule in 8a and the ethanol
solvate molecules (Table 2).
Compound 2 Yield 86%. Anal. Found: C, 55.4; H;
5.1; N, 2.3. Calc. for C29H31NOPRhCl2): C, 56.7; H,
5.1; N, 2.1%. 31P NMR: l=62.6 (d), (1J(RhꢀP)=145
1
Hz). H NMR: l=8.38–7.35 (m, 15H, C6H5), 1.44 (d,
15H, 4J=4 Hz, C5Me5). IR (cm−1): w(NH) 3306;
w(CO) 1674. FAB+ MS: 578, M+−Cl.
3. Conclusions
4.2. [RuCl2(p6-p-cymene)L]
The N-(diphenylphosphino)arylamides 3-NC5H4CO-
NHPPh2 and C6H5CONHPPh2 are P-monodentate in
cis-[PtCl2L2] and [MCl2(arene)L] (M=Rh, arene=h5-
C5Me5; M=Ru, arene=h6-p-cymene) while nickel(II)
is sufficiently hard to permit coordination by the amide
oxygen in [NiCl2L2]. Variations in NiꢀO bond lability
for 7, 8 suggests sensitivity of the carbonyl donor
capacity to the aryl substituent. Further studies on the
efficacy of L1,2 complexes in catalytic processes and the
preparation of P,O-chelates at the second- and
third-row d-block metals by halide abstraction using
silver(I) salts are underway.
A dichloromethane solution (1 cm3) of L (0.1 mmol)
was added to [{RuCl(m-Cl)(h6-p-cymene)}2] (0.05
mmol) in dichloromethane (1 cm3) and stirred for 24 h.
Vapour diffusion of diethyl ether into this solution gave
[RuCl2(h6-p-cymene)L] (L=L1 (3) or L2 (4)) as brown
crystals.
Compound 3 Yield 89%. Anal. Found: C, 54.3; H,
4.7; N, 4.1. Calc. for C28H29N2OPRuCl2: C, 54.9; H,
4.8; N, 4.5%. 31P NMR: l=60.6(s). 1H NMR l=
3
9.02–7.27 (m, 14H, aromatic H), 5.37 (d, 2H, J=8
3
Hz, C6H4), 5.24 (d, 2H, J=8 Hz, C6H4), 2.55 (septet,
3
i
3
i
1H, J=9 Hz, Pr), 0.86 (d, 6H, J=9 Hz, Pr). IR
(cm−1): w(NH) 3317; w(CO) 1682. FAB+ MS: 577,
M+−Cl.
4. Experimental
Compound 4 Yield 82%. Anal. Found: C, 56.1; H,
5.1; N, 2.2. Calc. for C29H30NOPRuCl2: C, 56.9; H, 4.9;
1
Preparations of 1–8 were conducted under aerobic
N, 2.3%. 31P NMR: l=58.9(s). H NMR: l=8.12–

P. Bhattacharyya et al. / Polyhedron 20 (2001) 1803–1808
1807
3
7.32 (m, 15H, C6H5), 5.35 (d, 2H, J=6 Hz, C6H4),
a DF map and allowed to refine subject to a distance
constraint. Structural refinements were by the full-ma-
trix least-squares method on F2 using the program
3
3
5.22 (d, 2H, J=6 Hz, C6H4), 2.52 (septet, 1H, J=9
Hz, C3H7), 0.85 (d, 6H, J=9 Hz, C3H7). IR (cm−1):
i
3
i
w(NH) 3324; w(CO) 1675. FAB+ MS: 576, M+−Cl.
SHELXTL-PC [26].
C29H31Cl2NOPRh, M=614.33, orthorhombic, a=
, ,
8.3541(1) A, b=17.9890(4), c=18.0726(1) A, V=
4.3. cis-[PtCl2L2]
3
,
2715.98(7)
A ,
F(000)=1256,
crystal
size
A dichloromethane solution (1 cm3) of L (0.1 mmol)
was added to [PtCl2(MeCN)2] (0.05 mmol) in
dichloromethane (1 cm3) and stirred for 24 h. Vapour
diffusion of diethyl ether into this solution gave cis-
[PtCl2L2] (L=L1 (5) or L2 (6)) as colourless crystals.
Compound 5 Yield 53%. Anal. Found: C, 48.2; H,
3.6; N, 6.2. Calc. for C36H30N4O2P2PtCl2: C, 49.2; H,
3.4; N, 6.4%. 31P NMR l=28.1(s), (1J(PtꢀP) 3849 Hz).
1H NMR: l=9.00–7.43 (m, aromatic H). IR (cm−1):
w(NH) 3213; w(CO) 1684. FAB+ MS: 843, M+−Cl.
Compound 6 Yield 86%. Anal. Found: C, 51.9; H,
3.7; N, 3.0. Calc. for C38H32N2O2P2PtCl2: C, 52.1; H,
3.7; N, 3.2%. 31P NMR: l=27.6(s), (1J(PtꢀP)=3876
Hz). 1H NMR l=7.84–7.18 (m, aromatic H). IR
(cm−1): w(NH) 3242; w(CO) 1686. FAB+ MS: 841,
M+−Cl.
0.1×0.2×0.3 mm, space group P212121, Z=4, v(Mo
Ka)=0.907 mm−1. Of 12003 measured data, 3893
were unique (Rint 0.1138) to give R1[I\2|(I)]=0.0344
and wR2=0.0549.
C82.5H84Cl4N4Ni2O7.5P4, M=1634.64, monoclinic,
,
a=17.4983(8), b=23.7288(13), c=20.7976(11) A, V=
3
,
8155.2(7) A , F(000)=3404, crystal size=0.12×
0.04×0.04 mm, space group P21/n, Z=4, v(Mo
Ka)=0.727 mm−1. Of 47742 measured data, 18833
were unique (Rint 0.3319) to give R1[I\2|(I)]=0.0977
and wR2=0.1132.
5. Supplementary materials
Crystallographic data for the structural analysis (2, 8)
has been deposited with the Cambridge Crystallo-
graphic Data Centre, CCDC Nos. 146548 and 146549.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: +44-1223-336033;
4.4. Reaction of L1,2 with NiCl2·6H2O
A solution of L (0.1 mmol) in dichloromethane (1
cm3) was added to nickel chloride hexahydrate (0.05
mmol) in ethanol (1 cm3), giving a turquoise solution
which was stirred for 24 h. The solvent was removed in
vacuo and the crude product extracted into ethanol (1
cm3). Vapour diffusion of diethyl ether into this solu-
tion gave [NiCl(EtOH)L2]·Cl·[NiCl2L2] as turquoise (L1
(7)) or green (L2 (8)) solids.
e-mail:
deposit@ccdc.cam.ac.uk
or
www:http://
www.ccdc.cam.ac.uk).
Acknowledgements
We are grateful to the EPSRC (P.B.) and EXXON
Chemicals (T.Q.L.) for financial support, Johnson
Matthey plc for the loan of precious metal salts and to
the J.R.E.I. for an equipment grant.
Compound 7 Yield 75%. Anal. Found : C, 55.5; H,
4.4; N, 7.1. Calc for C74H66N8P4O5Ni2Cl.43H2O: C,
56.1; H, 4.6; N, 7.1%. IR (cm−1): w(CO) 1618. FAB+
MS: 705, [NiClL12 ]+.
Compound 8 Yield 42%. Anal. Found: C, 60.9; H,
4.5; N, 3.4. Calc. for C78H70N4P4O5Ni2Cl4·CH3OH·
2C2H5OH: C, 60.4; H, 5.2; N, 3.4%. IR (cm−1): w(CO)
1604. FAB+ MS: 703, [NiClL22 ]+.
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