Late transition-metal complexes of [Ph2P(O)NP(E)Ph2]- (E = S or Se) with a P,N-hybrid ligand: Synthesis and structure

Article abstract of DOI:10.1039/a902738f

The unsymmetrical ligands [Ph₂P(O)NP(E)Ph₂]^- (E = S or Se) adopt a range of ligation modes (O,E-chelate, E-monodentate and as a non-co- ordinating anion) upon reaction with selected late transition-metal tertiary phosphine complexes. Hence treatment of cis-[PtCl₂(PPh₃)₂] with K[Ph₂P(O)NP(E)Ph₂] in methanol gave the expected six-membered O,E-chelate complexes [Pt(PPh₃)₂{Ph₂P(O)NP(E)Ph₂-O,E}]⁺ isolated as their hexafluorophosphate salts. When [Pt(Ph₂PC₆H₄NH₂-P,N)₂]Cl₂ was allowed to react under analogous conditions the monocationic mixed complexes [Pt(Ph₂PC₆H₄NH-P,N)(Ph₂PC₆H₄NH₂-P,N)][Ph₂P(O)NP(E)Ph₂] were obtained in excellent yields (>90%). Reaction of [Pd(Ph₂PC₆H₄NH₂-P,N)₂]Cl₂ with K[Ph₂P(O)NP(S)Ph₂] (1 : 2 molar ratio) gave a mixture of three products identified by ³¹P-{¹H} NMR as [Pd(Ph₂PC₆H₄NH-P,N) (Ph₂PC₆H₄NH₂- P,N)][Ph₂P(O)NP(S)Ph₂], [Pd(Ph₂PC₆H₄NH-P,N){Ph₂P(O)NP(S)Ph₂-O,S}] (P trans to O) and Ph₂PC₆H₄NH₂. Alternatively the neutral compound [Pd(Ph₂PC₆H₄NH-P,N){Ph₂P(O)NP(S)Ph₂-O,S}] was synthesised in moderate yield from [PdCl₂{Ph₂PC₆H₄NH₂-P,N)] and two equivalents of K[Ph₂P(O)NP(S)Ph₂]. Chloride metathesis of [Pt(X)Cl(Ph₂PC₆H₄NH₂-P,N)] (X = CH₃ or Cl) with K[Ph₂P(O)NP(E)Ph₂] gave a series of platinum(II) complexes [Pt(X){Ph₂P(O)NP(E)Ph₂-E}(Ph₂PC₆H₄NH₂-P,N)] (P trans to E) in which the anion adopts an E-monodentate co-ordination mode. The gold(i) complexes [AuCl(PPh₃)] and [AuCl(Ph:PC₆H·NH:)] undergo smooth substitution reactions with K[Ph₂P(O)NP(E)Ph₂] to give [Au{Ph₂P(O)NP(E)Ph₂- E}(PPh₃)] and [Au{Ph₂P(O)NP(E)Ph₂-E}(Ph₂PC₆H₄NH₂)] respectively. All new compounds have been characterised by a combination of multinuclear NMR [¹H, ³¹P-{¹H} and ¹⁹⁵Pt-{¹H}], IR spectroscopy and elemental analyses. The molecular structures of four examples have been determined by single-crystal X-ray crystallography and furthermore reveal intra- and inter- molecular PE···H-N hydrogen bonding arrangements. There is also evidence for π-delocalisation within the E-P-N-P-O backbone.

Full text of DOI:10.1039/a902738f

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Late transition-metal complexes of [Ph P(O)NP(E)Ph ]— (E = S or
2
2
Se) with a P,N-hybrid ligand: synthesis and structure
Alexandra M. Z. Slawin and Martin B. Smith*
Department of Chemistry, L oughborough University, L oughborough, L eics., UK L E11 3T U.
E-mail: m.b.smith=lboro.ac.uk
Received 3rd April 1999, Accepted 11th May 1999
The unsymmetrical ligands [Ph P(O)NP(E)Ph ]~ (E \ S or Se) adopt a range of ligation modes (O,E-chelate,
2
2
E-monodentate and as a non-co-ordinating anion) upon reaction with selected late transition-metal tertiary
phosphine complexes. Hence treatment of cis-[PtCl (PPh ) ] with K[Ph P(O)NP(E)Ph ] in methanol gave the
2
3 2
2
2
expected six-membered O,E-chelate complexes [Pt(PPh ) MPh P(O)NP(E)Ph -O,EN]` isolated as their
3 2
hexaÑuorophosphate salts. When [Pt(Ph PC H NH -P,N) ]Cl was allowed to react under analogous conditions
2
2
2
6
4
2
2
2
the monocationic mixed complexes [Pt(Ph PC H NH-P,N)(Ph PC H NH -P,N)][Ph P(O)NP(E)Ph ] were
2
6
4
2
4
6
2
4
2
2
2
2
obtained in excellent yields ([90%). Reaction of [Pd(Ph PC H NH -P,N) ]Cl with K[Ph P(O)NP(S)Ph ] (1 : 2
2
6
2
2
6 4
2
molar ratio) gave a mixture of three products identiÐed by 31P-M1HN NMR as [Pd(Ph PC H NH-P,N)
2
(Ph PC H NH -P,N)][Ph P(O)NP(S)Ph ], [Pd(Ph PC H NH-P,N)MPh P(O)NP(S)Ph -O,SN] (P trans to O) and
2
2
6
4
4
2
2
2
2
2
6
4
2
2
Ph PC H NH . Alternatively the neutral compound [Pd(Ph PC H NH-P,N)MPh P(O)NP(S)Ph -O,SN] was
6
2
6
4
2
2
synthesised in moderate yield from [PdCl (Ph PC H NH -P,N)] and two equivalents of K[Ph P(O)NP(S)Ph ].
2
4
2
6
4
2
2
2
Chloride metathesis of [Pt(X)Cl(Ph PC H NH -P,N)] (X \ CH or Cl) with K[Ph P(O)NP(E)Ph ] gave a series
2
6
2
3
2
2
of platinum(II) complexes [Pt(X)MPh P(O)NP(E)Ph -EN(Ph PC H NH -P,N)] (P trans to E) in which the anion
2
2
2
6
4
2
adopts an E-monodentate co-ordination mode. The gold(I) complexes [AuCl(PPh )] and [AuCl(Ph PC H NH )]
3
2
6
4
2
undergo smooth substitution reactions with K[Ph P(O)NP(E)Ph ] to give [AuMPh P(O)NP(E)Ph -EN(PPh )] and
[AuMPh P(O)NP(E)Ph -EN(Ph PC H NH )] respectively. All new compounds have been characterised by a
combination of multinuclear NMR [1H, 31P-M1HN and 195Pt-M1HN], IR spectroscopy and elemental analyses. The
molecular structures of four examples have been determined by single-crystal X-ray crystallography and
furthermore reveal intra- and inter-molecular PEÉ É ÉHÈN hydrogen bonding arrangements. There is also evidence
for p-delocalisation within the EÈPÈNÈPÈO backbone.
2
2
2
2
3
2
2
2
6
4
2
NP(E)Ph -EN ] (en \ H NCH CH NH ).1e It is tempting to
Introduction
2
2
2
2
2
2
suggest from these sparse examples alone that the
The co-ordination chemistry of [R P(E)NP(E)R ]~ has of late
[R P(O)NP(E)R ]~ bonding mode adopted may be inÑu-
2
2
2
2
received much attention principally because of its close associ-
ation with acetylacetonate (acac).1 Whereas extensive work
has focused on symmetrical systems (E \ O, S or Se) there has
been considerably less documentation regarding the asym-
metrical ligands [R P(O)NP(E)R ]~ [E \ S I; E \ Se II]
enced by the spectator ligand present within the metal co-
ordination sphere. We therefore were interested to probe what
ligation modes would be adopted using a hybrid ligand
bearing
a
P,N-donor set. Numerous studies with
Ph PC H NH , incorporating both tertiary phosphine and
2
2
2
6
4
2
bearing both ““hardÏÏ and ““softÏÏ donor atoms.1dhf,2h6 More-
over several complexes of [R P(E)NP(E)R ]~ have found
primary amine functionalities, have been described with
several complexes Ðnding important uses in catalysis and as
antitumour agents.11
2
2
important applications as NMR shift reagents,7 selective
metal extractants8 and in catalysis.9 Clearly an appreciation
of the co-ordinating capabilities of these ligands towards
metals and their subsequent reactivity is important given that
complexes of acac (and its analogues) are useful in several
metal complex catalysed reactions.10
In recent studies we have observed three di†erent binding
Herein we report the Ðrst examples of PdIIÈ, PtIIÈ and
AuIPh PC H NH complexes with [Ph P(O)NP(E)Ph ]~
modes for [R P(O)NP(E)R ]~ (R \ Ph) at various late
2
2
2
6
4
2
2
2
transition-metal centres (Chart 1, AÈC), the most prevalent
being O,E-chelation, e.g. [PdL MPh P(O)NP(E)Ph -O,EN]PF
including their synthesis and characterisation. Furthermore
we demonstrate a range of bonding modes for [Ph P-
2
2
2
6
2
(O)NP(E)Ph ]~ including O,E-chelation, E-monodendate and
2
(L \ PPh ; 2L \ Ph PCH CH PPh
or cis-Ph PCH2
3
2
2
2
2
2
2
CHPPh ).1f The [R P(O)NP(E)R ]~ anion can also behave
the Ðrst example of [Ph P(O)NP(E)Ph ]~ acting as a non-co-
2
2
2
2
as an E-monodentate bound ligand, e.g. [Pd(en)MPh P(O)-
ordinating anion (D). The crystal structures of
2
New J. Chem., 1999, 23, 777È783
777

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[Pt(Ph PC H NH-P,N)(Ph PC H NH -P,N)][Ph P(O)NP-
P,N)][Ph P(O)NP(S)Ph ] 5, [Pd(Ph PC H NH-P,N)MPh P-
2
6
4
2
6
4
2
2
2
2
2
6
4
2
(Se)Ph ], [Pd(Ph PC H NH-P,N)MPh P(O)NP(S)Ph -O,SN],
(O)NP(S)Ph -O,SN] 6 and Ph PC H NH .
2
2
6
4
2
2
2
2
6
4
2
[Pt(CH )MPh P(O)NP(S)Ph -SN(Ph PC H NH -P,N)]
and
3
2
2
2
6
4
2
[AuMPh P(O)NP(S)Ph -SN(Ph PC H NH )] have been deter-
mined.
[Pd(Ph PC H NH-P,N){Ph P(O)NP(S)Ph -O,S} ], 6. To
2
2
2
6
4
2
2
6
4
2
6
2
a suspension of [PdCl (Ph PC H NH -P,N)] (0.030 g, 0.066
2
in CH OH
3
2
4
2
mmol)
(1
cm3)
was
added
solid
K[Ph P(O)NP(S)Ph ] (0.064 g, 0.136 mmol). The yellow solid
Experimental
General procedures
2
2
dissolved to give an orange solution whereupon an orange
solid formed within ca. 1È2 min. The mixture was stirred for 1
h and the product collected by suction Ðltration, washed with
All reactions were carried out in air using previously distilled
or HPLC grade solvents. The ligands [Ph P(O)NP(E)Ph ]~
CH OH (ca. 0.5 cm3) and dried in vacuo. Yield: 0.026 g, 48%.
3
2
2
FAB` MS: m/z 815 (M`). IR: 3378 (l ), 576 (l ). 1H NMR:
(E \ S or Se)4 were prepared according to a literature method
NH
PS
d 7.91È6.28 (arom. H, NH). Slow di†usion of CH OH into a
as
were
[AuCl(Ph PC H NH )]11b
and
[M(X)Cl-
3
CDCl solution of 6 over the course of several days gave crys-
3
2
6
4
2
(Ph PC H NH -P,N)] (M \ Pt or Pd, X \ Me or Cl).11c The
complexes [M(Ph PC H NH -P,N) ]Cl , cis-[PtCl (PPh ) ]
and [AuCl(PPh )] were prepared from [MCl (cod)] (M \ Pd,
Pt; cod \ cycloocta-1,5-diene) or [AuCl(tht)] (tht \ tetra-
hydrothiophene) and the appropriate stoichiometry of tertiary
phosphine in CH Cl .
2
6
4
2
tals suitable for X-ray crystallography.
2
6
4
2
2
2
2
3 2
3
2
[Pt(CH ){Ph P(O)NP(S)Ph -S}(Ph PC H NH -P,N)], 7.
3
2
2
2
6
4
4
2
To a suspension of [Pt(CH )Cl(Ph PC H NH -P,N)] (0.041
3
2
6
2
g, 0.0784 mmol) in CH OH (1 cm3) was added solid
K[Ph P(O)NP(S)Ph ] (0.041 g, 0.0869 mmol). After stirring
the mixture for 1 h, the product was collected by suction Ðl-
3
2
2
Infrared spectra were recorded as KBr pellets in the range
4000È200 cm~1 on a PerkinÈElmer System 2000 Fourier-
transform spectrometer, 1H NMR spectra (250 MHz) on a
Bruker AC250 FT spectrometer with chemical shifts (d) in
2
2
tration, washed with a small portion of CH OH (ca. 0.5 cm3)
3
and dried in vacuo. Yield: 0.057 g, 79%. FAB`MS: m/z 920
(M`). IR: 3291, 3262 (l ), 571 (l ). 1H NMR: d 7.68È6.93
ppm to high frequency of SiMe and coupling constants (J) in
NH
PS
4
(arom. H), 6.51 [NH , 2J(PtH) 28.8 Hz], 0.01 [CH , 2J(PtH)
Hz, 31P-M1HN NMR spectra (36.2 MHz) were recorded on a
JEOL FX90Q spectrometer with chemical shifts (d) in ppm to
high frequency of 85% H PO and coupling constants (J) in
Hz and 195Pt-M1HN NMR spectra (53.7 MHz) were recorded
on a Bruker AC250 FT NMR spectrometer with d referenced
to external H PtCl (in D OÈHCl). All NMR spectra were
2
3
75.0 Hz, 3J(PH) 3.5 Hz]. Slow di†usion of CH OH into a
3
CDCl solution of 7 over the course of several days gave crys-
3
3
4
tals suitable for X-ray crystallography.
In a similar manner the following complexes were prepared:
[Pt(CH )MPh P(O)NP(Se)Ph -SeN(Ph PC H NH -P,N)]
8
3
2
2
2
6
4
2
2
6
2
(80%), FAB`MS: m/z 967 (M`). IR: 3289 (l ), 537 (l ). 1H
measured in CDCl unless otherwise stated. Elemental
analyses (PerkinÈElmer 2400 CHN elemental analyzer) were
NH
PSe
3
NMR: d 7.98È6.93 (arom. H), 6.45 [NH , 2J(PtH) 28.8 Hz],
2
[0.1 [CH , 2J(PtH) 74.8 Hz, 3J(PH) 3.5 Hz]. [PtClMPh P-
performed by the Loughborough University Analytical
Service within the Department of Chemistry.
Precious metal salts were provided on loan by Johnson
Matthey plc.
3
2
(O)NP(S)Ph -SN(Ph PC H NH -P,N)] 9 (99%), FAB`MS:
2
2
6
4
2
m/z 940 (M`). IR: 3442 (l ), 570 (l ), 298 (l ). 1H NMR: d
NH PS PtCl
8.40È7.12 (arom. H, NH ). [PtClMPh P(O)NP(Se)Ph -
2
2
2
SeN(Ph PC H NH -P,N)] 10 (95%), FAB`MS: m/z 987 (M`).
2
6
4
2
IR: 3442 (l ), 537 (l ), 297 (l ). 1H NMR: d 8.13È7.14
Syntheses
NH
(arom. H, NH ).
2
PSe
PtCl
[Pt(PPh ) {Ph P(O)NP(S)Ph -O,S} ]PF , 1. To the solids
3 2
2
2
6
cis-[PtCl (PPh ) ]
3 2
K[Ph P(O)NP(S)Ph ] (0.047 g, 0.0997 mmol) was added
(0.071
g,
0.0898
mmol)
and
[Au{Ph P(O)NP(S)Ph -S}(PPh )], 11. To a suspension of
2
2
2
3
[AuCl(PPh )] (0.034 g, 0.0687 mmol) in CH OH (0.5 cm3) was
2
2
3
3
CH OH (2.5 cm3). After stirring for 150 min, the solution was
Ðltered and [NH ][PF ] (0.043 g) in CH OH (minimum
volume) added. The white solid was collected by suction Ðl-
added solid K[Ph P(O)NP(S)Ph ] (0.033 g, 0.0670 mmol).
3
2
2
The suspension dissolved and after ca. 5 min a white solid
formed. The mixture was stirred for 20 min, the product col-
lected by suction Ðltration, washed with a small portion of
4
6
3
tration and dried in vacuo. Yield: 0.101 g, 87%. IR: 575 (l ).
PS
1H NMR: d 7.67È7.06 (arom. H). In a similar manner
CH OH (ca. 0.5 cm3) and dried in vacuo. Compounds 11 (and
3
[Pt(PPh ) MPh P(O)NP(Se)Ph -O,SeN]PF 2 was prepared
12) may be recrystallised from CH Cl ÈEt OÈlight petroleum
3 2
2
2
6
2
2
2
(90%). IR: 547 (l ). 1H NMR: d 7.73È7.05 (arom. H).
(bp 60È80 ¡C). Yield: 0.044 g, 69%. IR: 564 (l ). 1H NMR: d
8.04È7.01 (arom. H).
PSe
PS
[Pt(Ph PC H NH-P,N)(Ph PC H NH -P,N)] [Ph P(O)-
In a similar manner the following complexes were prepared:
2
2
6
4
2
6
4
2
2
6
2
NP(S)Ph ], 3. To the solids [Pt(Ph PC H NH -P,N) ]Cl
[AuMPh P(O)NP(Se)Ph -SeN(PPh )] 12 (80%), IR: 553 (l ).
4
2
2
2
2
2
3
PSe
(0.052 g, 0.0634 mmol) and K[Ph P(O)NP(S)Ph ] (0.063 g,
1H NMR: d 8.10È7.03 (arom. H). [AuMPh P(O)NP(S)Ph -
2
2
2
2
0.134 mmol) was added CH OH (1 cm3). The resulting bright
yellow suspension was stirred for ca. 1 h. The solid was col-
SN(Ph PC H NH )] 13 (91%), IR: 3424, 3298, 3168 (l ), 561
3
2
6
4
2
NH
(l ). 1H NMR:
d
8.09È6.37 (arom. H), 4.64 (NH ).
PS
2
lected by suction Ðltration, washed with CH OH (ca. 0.5 cm3)
[AuMPh P(O)NP(Se)Ph -SeN(Ph PC H NH )] 14 (93%), IR:
3
and dried in vacuo. Yield: 0.074 g, 99%. IR: 3666 (l ), 3386,
OH
2
2
2
6
4
2
3416, 3295, 3155 (l ), 557 (l ). 1H NMR: d 8.05È6.46 (arom.
NH
PSe
3341, 3221 (l ), 594 (l ). 1H NMR: d 8.08È6.58 (arom. H,
H), 4.67 (NH ).
NH
PS
2
NH, NH ). The CH OH Ðltrate was examined by 31P-M1HN
Crystals of 13 suitable for X-ray crystallography were
obtained by slow evaporation of a CH OHÈCDCl solution
over ca. 2 months.
2
3
NMR and showed Ph P(O)NHP(S)Ph as the only phos-
phorus containing species present.
2
2
3
3
In a similar manner the following complex was prepared:
Microanalytical and selected spectroscopic data are given in
Tables 1 and 2.
[Pt(Ph PC H NH-P,N)(Ph PC H NH -P,N)][Ph P(O)NP-
2
6
4
2
6
4
2
2
(Se)Ph ] 4 (92%), IR: 3665 (l ), 3388, 3334, 3221 (l ), 552
OH NH
(l ). 1H NMR: d 8.08È6.61 (arom. H, NH, NH ). Slow di†u-
PSe
2
X-Ray crystallography
2
sion of CH OH into a CDCl solution of 4 over the course of
several days gave crystals suitable for X-ray crystallography.
3
3
The crystal structures of compounds 4, 6, 7 and 13 were
obtained using a Bruker SMART di†ractometer with
graphite-monochromated Mo-Ka radiation (j \ 0.710 73 A).
Details of the crystal data collections and reÐnements are
The reaction of I with [Pd(Ph PC H NH -P,N) ]Cl under
2
6
4
2
2
2
analogous conditions gave a mixture of three phosphorus con-
taining species: [Pd(Ph PC H NH-P,N)(Ph PC H NH -
2
6
4
2
6
4
2
778
New J. Chem., 1999, 23, 777È783

View Article Online
Table 1 Microanalytical data for compounds 1È4, 6È14 (calculated
All non H-atoms in the structures were reÐned anisotropi-
cally including the solvent in 4 although the protons were not
located on this 1/2 weight CH OH. In 7 the 1/4 weight CHCl
was reÐned isotropically. All NÈH H atoms were located and
reÐned isotropically. All other protons were reÐned in ideal-
ised geometries with a riding model. ReÐnements converged to
the residuals given in Table 3. All calculations were made with
programs of SHELXTL systems.
values in parentheses)
Analysis (%)
3
3
Compound
C
H
N
1
2
55.05 (55.55)
53.45 (53.60)
60.15 (60.70)
58.10 (58.40)
61.20 (61.90)
55.95 (56.15)
52.60 (53.40)
53.25 (53.65)
50.70 (51.10)
56.20 (56.55)
53.20 (53.75)
55.35 (55.65)
52.75 (52.90)
3.80 (3.90)
3.65 (3.75)
4.35 (4.45)
3.85 (4.30)
4.00 (4.35)
4.20 (4.30)
3.95 (4.05)
3.65 (3.85)
3.45 (3.70)
3.95 (3.95)
3.50 (3.75)
3.75 (4.00)
3.60 (3.80)
1.00 (1.10)
1.00 (1.05)
3.40 (3.50)
3.20 (3.40)
3.55 (3.45)
3.05 (3.05)
2.85 (2.90)
3.20 (3.00)
3.00 (2.85)
1.20 (1.55)
1.10 (1.50)
3.25 (3.10)
3.30 (2.95)
3a
4a
6
CCDC reference number 440/116. See http://www.rsc.org/
suppdata/nj/1999/777/ for crystallographic Ðles in .cif format.
7
8
Results and discussion
The reaction of [PtCl L ] (L \ tertiary phosphine) with the
9
10
11
12
13
14
2 2
symmetrical anions [R@ P(E)NP(E)R@ ]~ (R@ \ Ph or OPh;
2
2
E \ S or Se) has been shown to give [PtMR@ P(E)NP(E)R@ -
2
2
E,E@NL ]`.14
We
Ðnd
that
transmetallation
of
2
K[Ph P(O)NP(E)Ph ] (E \ S I; E \ Se II) with cis-
[PtCl (PPh ) ] (ca. 1:1 molar ratio) in methanol likewise
a Calculated for 3, 4 É 0.5CH OH.
2
2
2
3
3 2
a†ords the O,E-chelate cationic complexes [PtMPh P-
2
(O)NP(E)Ph -O,EN(PPh ) ]` (E \ S 1; E \ Se 2), isolated as
2
3 2
given in Table 3. Intensities were collected using 0.3¡ or 0.15¡
width u steps accumulating area detector frames spanning a
hemisphere of reciprocal space for all structures (data were
integrated using the SAINT12 program). Structures were
solved by direct methods and reÐned by full matrix least
squares against F2 of all data using SHELXTL software.13a
Absorption corrections were performed on the basis of multi-
ple equivalent reÑections using the SADABS program.13b
their hexaÑuorophosphate salts. Compounds 1 and 2 are akin
to the known palladium(II) salts [PdMPh P(O)NP(E)Ph -
2
2
O,EN(PPh ) ]PF .1f The spectroscopic and analytical data
3 2
6
for these platinum(II) complexes are unremarkable (Tables 1, 2
and Experimental section). As expected the magnitude of
1J(PtP) is reduced by ca. 400 Hz [3246 Hz for 1 (P trans to S);
3207 Hz for 2 (P trans to Se)] in comparison with cis-
[PtCl (PPh ) ] [1J(PtP) 3673 Hz] but increased by ca. 350
2
3 2
Table 2 Selected NMR data (d in ppm, J in Hz) for compounds 1È14
Compound
d(PR )a
J(PtP)
d(P )b
J(PtP )
d(P )
J(PP)
20
J(PSe)
d(Pt)
3
E
E
O
1
2
21.0
8.8c
20.3
7.0c
3246
4020
3207
4025
3123
3136
28.6
72
84
32.8
[4298
[4342
16.6
34.2
18
477
651
3
4
27.5
27.4
44.7d
53.6
26.9
26.7
23.5
23.3
37.3
37.9
25.2
25.8
38.2
26.0
34.8
32.0
18.2
14.2
29.5
15.5
27.4
14.9
27.0
14.5
14.2
14.3
12.8
27.3
15.6
16.6
17.3
18.4
12.1
12.7
12.2
13.0
[4497
[4491
5
6
7
4219
4170
3501
3448
96
97
66
75
6.6
6.0
9.0
8.5
[4291
[4319
[3748
[3783
8
525
518
462
467
9
10
11
12
13
14
a PR \ Ph PC H NH or PPh . b E \ S or Se. c P trans to O [no J(PtP ) coupling observed (36.2 MHz)]. d Sample also contained 6 and
3
2
6
4
2
3
O
Ph PC H NH .
2
6
4
2
Table 3 Details of the X-ray data collections and reÐnements for 4 É 0.5CH OH, 6, 7 É 0.25CHCl and 13
3
3
Compound
4 É 0.5CH OH
6
7 É 0.25CHCl
13
3
3
Empirical formula
C
H
N OP PtSe É 0.5CH OH
C
815.09
Triclinic
9.8531(3)
13.4561(4)
15.5289(5)
102.9820(10)
94.7740(10)
110.6100(10)
1847.9(1)
293(2)
H
N OP PdS
C
949.66
Triclinic
H
N OP PtS É 0.25CHCl
C
906.66
H AuN OP S
60 51
3
4
3
42 35
2
3
43 39
2
3
3
42 36
2
3
M
1243.99
Triclinic
Crystal system
Triclinic
9.0446(3)
11.5989(3)
19.1145(6)
91.8030(10)
95.2790(10)
104.4790(10)
1930.2(1)
293(2)
P1
2
4.024
6880
a/A
b/A
c/A
a/¡
13.3168(6)
13.4648(6)
18.2628(8)
109.01(1)
96.1290(10)
113.8590(10)
2721.6(2)
293(2)
P1
2
3.409
12436
10.7499(3)
13.9705(4)
16.7686(4)
112.0190(10)
99.4310(10)
98.6350(10)
2240.6(1)
293(2)
P1
2
3.362
11568
b/¡
c/¡
V /A
Ž
3
T /K
Space group
Z
k/mm~1
P1
2
0.725
8374
ReÑections collected
Independent reÑections
Final R indices
[I [ 2p(I)]
7564[R(int) \ 0.0369]
5236[R(int) \ 0.0378]
6429[R(int) \ 0.0439]
5133[R(int) \ 0.0299]
R1 \ 0.0359, wR2 \ 0.0824
R1 \ 0.0490, wR2 \ 0.1157
R1 \ 0.0438, wR2 \ 0.0994
R1 \ 0.0413, wR2 \ 0.1006
New J. Chem., 1999, 23, 777È783
779

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Table 4 Selected bond distances (A) and angles (¡) for compound 4
Hz when P is disposed trans to O (4020 Hz for 1; 4025 Hz for
2).
Pt(1)ÈN(2)
Pt(1)ÈN(20)
Pt(1)ÈP(1)
Pt(1)ÈP(2)
2.008(5)
2.108(5)
2.239(2)
2.241(2)
Se(3)ÈP(3)
P(3)ÈN(3)
N(3)ÈP(4)
P(4)ÈO(4)
2.140(2)
1.572(6)
1.563(6)
1.520(5)
When [Pt(Ph PC H NH -P,N) ]Cl
[prepared from
2
6
4
2
2
2
[PtCl (cod)] (cod \ cycloocta-1,5-diene) and 2 equivalents of
2
Ph PC H NH ] was allowed to react in a 1 : 2 molar ratio
2
6
4
2
N(2)ÈPt(1)ÈN(20)
N(2)ÈPt(1)ÈP(1)
N(20)ÈPt(1)ÈP(1)
N(2)ÈPt(1)ÈP(2)
N(20)ÈPt(1)ÈP(2)
89.5(2)
83.3(2)
172.7(2)
174.0(2)
84.6(2)
P(1)ÈPt(1)ÈP(2)
Se(3)ÈN(3)ÈP(3)
P(3)ÈN(3)ÈP(4)
N(3)ÈP(4)ÈO(4)
102.61(6)
119.6(2)
149.9(4)
120.5(3)
with I (or II) in methanol under similar conditions, the bright
yellow solids [Pt(Ph PC H NH-P,N)(Ph PC H NH -
P,N)][Ph P(O)NP(E)Ph ] (E \ S 3; E \ Se 4) were obtained
2
6
4
2
6
4
2
2
2
in excellent yields ([90%). The 31P-M1HN NMR spectra of 3
(and 4) both show a single d(P) resonance at ca. d 27 with a
1J(PtP) of 3123 Hz (for 3) and 3136 Hz (for 4). It has pre-
viously been reported11j that [Pt(Ph PC H NH -P,N) ]Cl
2
6
4
2
2
2
undergoes double deprotonation with base to give the neutral
Ðve-membered PtÈPÈCÈCÈN metallacycles embody a P,N-
chelating Ph PC H NH ligand and deprotonated
bis(amido) complex [Pt(Ph PC H NH-P,N) ] with a negligi-
a
2
6
4
2
2
6
4
2
ble change in d(P) but a reduction in 1J(PtP) from 3343 to
3032 Hz respectively. The di†erences in 1J(PtP) reÑect the
trans inÑuence of an amine versus amido ligand. The observed
1J(PtP) values of ca. 3130 Hz for 3 (and 4) suggest that one
co-ordinated Ph PC H NH ligand has been deprotonated.
[Ph PC H NH]~ ligand. The Pt(1)ÈP(1), Pt(1)ÈP(2), Pt(1)È
2
6 4
N(2) and Pt(1)ÈN(20) bond lengths are comparable to those
reported in the bis-homoleptic species [PtMPh PC H NH -
2
6
4 2
The
P,NN ]2`
and
[PtMPh PC H NH-P,NN ].11l,11m
2
2
6
4
2
[Ph P(O)NP(Se)Ph ]~ anion is involved in hydrogen
2
6
4
2
2
2
Hence the co-ordination sphere around the platinum(II) centre
embraces a chelating Ph PC H NH and [Ph PC H NH]~
bonding with the NH protons of the cis co-ordinated ligands
[N(2)É É ÉSe(3) 3.79 A, H(2A)É É ÉSe(3) 3.04 A, N(2)ÈH(2A)É É ÉSe(3)
134; N(20)É É ÉO(4) 2.75 A, H(20B)É É ÉO(4) 1.89 A, N(20)È
H(20B)É É ÉO(4) 146¡]. This e†ectively twists the O(4)ÈP(4)È
2
6
4
2
2
6 4
ligand, the latter deprotonated by [Ph P(O)NP(E)Ph ]~.
Indeed upon examination of the methanolic Ðltrate by 31P-
M1HN NMR, only the protonated phosphorus(V) compounds
Ph P(O)NHP(E)Ph were observed whose NMR data match
2
2
N(3)ÈP(3)ÈSe(3) fragment to adopt
a syn conformation
thereby forcing the OÉ É ÉSe donor atoms closer together
(OÉ É ÉSe contact 4.15 A). In contrast Ph P(Se)NHP(Se)Ph has
2
2
those previously reported.4 The counterion in 3 (and 4) is the
2
2
[Ph P(O)NP(E)Ph ]~ anion whose similarity in d(P) with
an approximate anti disposition of the two selenium atoms
with the molecules associated by NÈHÉ É ÉSe hydrogen bonds
to form dimer pairs.15 Within the uncomplexed anion, the
P(3)ÈN(3)ÈP(4) angle is substantially enlarged [149.9(4)¡] with
respect to when [Ph P(O)NP(E)Ph ]~ adopts a O,E-chelat-
2
2
that reported for I and II supports a non-co-ordinating role
[further corroborated by the absence of any J(PtP)].4
2
2
ing, E-bridging or E-monodentate bonding mode.1dhf,2h6 To
the best of our knowledge this represents the Ðrst crystal
structure of a [Ph P(O)NP(Se)Ph ]~ anion with a transition-
2
2
metal
complex
cation.
The
potassium
ion
in
K[Ph P(S)NP(S)Ph ] can readily be exchanged by other
2
2
cations as earlier documented.16 Interestingly the PÈNÈP
angle in [Ph P(S)NP(S)Ph ]~ varies markedly from 128.6(2)¡
(for K`) to 180¡ [for N(PPh ) `].
The analogous reaction of [Pd(Ph PC H NH -P,N) ]Cl
with I was also studied. A dark orange solid was isolated
whose 31P-M1HN NMR spectrum revealed one predominant
species, [Pd(Ph PC H NH-P,N)(Ph PC H NH -P,N)][Ph -
P(O)NP(S)Ph ] 5. In addition two minor species were also
present and identiÐed as the neutral compound [Pd(Ph PC -
2
2
3 2
2
6
4
2
2
2
In the crystal structure of 4 (Table 4 and Fig. 1) the
platinum(II) centre is cis co-ordinated by two P,N-didentate
2
6
4
2
6
4
2
2
2
ligands arranged in
a slightly distorted square planar
2
6
6 4
H NH-P,N)MPh P(O)NP(S)Ph -O,SN] 6 and free Ph PC H -
geometry [N(2)ÈPt(1)ÈP(1) 83.3(2), N(20)ÈPt(1)ÈP(2) 84.6(2),
N(2)ÈPt(1)ÈN(20) 89.5(2), P(1)ÈPt(1)ÈP(2) 102.61(6)¡]. The two
4
2
2
2
NH [d(P) [19.7]. Independently 6 was isolated in modest
2
yield from [PdCl (Ph PC H NH -P,N)] and two equivalents
2
2
6
4
2
of K[Ph P(O)NP(S)Ph ]. The [Ph P(O)NP(S)Ph ]~ anion
2
2
2
2
acts as an O,E-chelating ligand whereas the second equivalent
presumably behaves as a base since examination of the Ðltrate
by 31P-M1HN NMR reveals only the neutral species
Ph P(O)NHP(S)Ph . In accordance with the structure
2
2
depicted, the 31P-M1HN NMR spectrum of 6 shows three single
resonances at d(P) 53.6, 32.0 and 27.3 consistent with three
inequivalent nuclei and only one isomer present in CDCl
3
solution. The downÐeld shift at d 53.6 corresponds to the P(III)
centre within the Ðve-membered MÈPÈCÈCÈN chelate ring.
The other 31P chemical shifts are indicative of O,S-chelation
and similar to those reported elsewhere.1f,4
To conÐrm the structure of compound 6 and to establish
unambiguously which isomer was formed we carried out a
single crystal X-ray di†raction study (Fig. 2, Table 5). This
reveals that two anionic ligands are co-ordinated in a diden-
tate mode around the palladium centre [maximum deviation
of 0.06 A for Pd out of the plane of its four substituents] with
O(2) trans to P(3) of the chelating amido ligand. The S(1)È
P(1)ÈN(1)ÈP(2)ÈO(2) fragment is approximately planar and is
hinged with respect to the co-ordination plane [i.e. along the
S(1)É É ÉO(2) vector] by 39¡. Within the S(1)ÈP(1)ÈN(1)ÈP(2)È
Fig. 1 Crystal structure of [Pt(Ph PC H NH-P,N)(Ph PC H NH -
2
6
4
2
6
4
2
P,N)][Ph P(O)NP(Se)Ph ] É 0.5CH OH 4 (CÈH hydrogen atoms and
2
2
3
solvent molecule omitted for clarity).
780
New J. Chem., 1999, 23, 777È783

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[Ph P(O)NP(E)Ph ]~ in which the ligand adopts a E-
2
2
Fig. 2 Crystal structure of [Pd(Ph PC H NH-P,N)MPh P(O)-
unidentate co-ordination mode.
2
6
4
2
NP(S)Ph -O,SN] 6 (CÈH hydrogen atoms omitted for clarity).
The molecular structure of 7 has also been determined (Fig.
3, Table 6). The platinum metal centre has a distorted square
planar co-ordination geometry with angles about the metal
centre of C(50)ÈPt(1)ÈS(2) 82.6(2), N(14)ÈPt(1)ÈP(1) 84.3(2),
C(50)ÈPt(1)ÈP(1) 92.9(3) and N(14)ÈPt(1)ÈS(2) 100.2(2)¡. Fur-
thermore the arrangement of the ligands around the metal is
such that the methyl group is trans to the amino group of the
2
O(2) ring there is evidence for electron delocalisation with long
PÈS and short PÈN bond distances. The PÈO bond length
in 6 is 1.502(4) A which can be compared to those observed
in the non-co-ordinating but strongly POÉ É ÉHÈN hydrogen
bonded Ph P(O)NHP(S)Ph [1.491(4) and 1.514(4) A].3
2
2
Reaction of [Pt(X)Cl(Ph PC H NH -P,N)] with I (or II)
2
6
4
2
(2 : 1 molar ratio) in methanol gave instead the platinum(II)
complexes [Pt(X)MPh P(O)NP(E)Ph -EN(Ph PC H NH -
P,N)] [X \ CH , E \ S 7; X \ CH , E \ Se 8; X \ Cl,
2
2
2
6
4
2
3
3
E \ S 9; X \ Cl, E \ Se 10]. The spectroscopic and micro-
analytical data (see Table 1 and 2, Experimental section) rein-
force in all cases the formation of a single isomer in which
[Ph P(O)NP(E)Ph ]~ is monodentate bound through the soft
2
2
E-donor centre. The 31P-M1HN NMR spectra for 7 and 8 show
a small downÐeld shift of ca. 5 ppm for the co-ordinated
Ph PC H NH ligand and a reduced 1J(PtP) of ca. 500 Hz
2
6
4
2
relative to [Pt(CH )Cl(Ph PC H NH -P,N)] [d(P) 20.6,
3
2
6
4
2
1J(PtP) 4716 Hz]. For compounds 9 and 10, there is a very
small downÐeld shift of ca. 1 ppm for the co-ordinated
Ph PC H NH ligand and a reduced 1J(PtP) of ca. 400 Hz
2
6
4
2
relative to [PtCl (Ph PC H NH -P,N)][d(P) 22.2, 1J(PtP)
2
2
6
3 2
4
2
3906 Hz, recorded in (CH ) SOÈ(CD ) SO]. The PO group
3 2
was typically observed around d(P) 15È18 indicative of a
““danglingÏÏ phosphorus(V) moiety. No evidence for isomer-
isation (e.g. to III) was observed even after allowing CDCl
Fig. 3 Crystal
structure
of
[Pt(CH )MPh P(O)NP(S)Ph -
3
3
2
2
solutions of 7 (or 8) to stand for up to 14 d. Addition of con-
SN(Ph PC H NH -P,N)] É 0.25CHCl 7 (CÈH hydrogen atoms and
2
6
4
2
3
solvent molecule omitted for clarity).
centrated HCl to a CDCl solution of 8 and monitoring the
3
reaction by 31P-M1HN NMR revealed the formation of
[PtCl (Ph PC H NH -P,N)] and Ph P(O)NHP(S)Ph . No
2
2
6
4
2
2
2
attempts to test for methane formation were pursued. Unlike
Table 6 Selected bond distances (A) and angles (¡) for compounds 7
and 13
the reaction of I with [PdCl (Ph PC H NH -P,N)] to give
2
2
6
4
2
6 the chelating amine proton in 9 and 10 has not under-
gone deprotonation and no evidence for species
such as [PtCl(Ph PC H NH-P,N)MPh P(O)NP(E)Ph -EN]~
7 (M \ Pt)
13 (M \ Au)
M(1)ÈP(1)
M(1)ÈS(2)
S(2)ÈP(2)
P(2)ÈN(2)
N(2)ÈP(3)
P(3)ÈO(3)
Pt(1)ÈC(50)
Pt(1)ÈN(14)
2.197(2)
2.372(2)
2.030(3)
1.574(6)
1.589(6)
1.492(5)
2.063(8)
2.153(6)
2.286(2)
2.319(2)
2.065(3)
1.579(6)
1.615(7)
1.507(5)
2
6
4
2
2
or [Pt(Ph PC H NH-P,N)MPh P(O)NP(E)Ph -O,EN] was ob-
2
6
4
2
2
served by 31P-M1HN NMR spectroscopy. Compounds
7
and 8 are the Ðrst examples of organometallic complexes of
Table 5 Selected bond distances (A) and angles (¡) for compound 6
P(1)ÈM(1)ÈS(2)
M(1)ÈS(2)ÈP(2)
S(2)ÈP(2)ÈN(2)
P(2)ÈN(2)ÈP(3)
N(2)ÈP(3)ÈO(3)
C(50)ÈPt(1)ÈS(2)
N(14)ÈPt(1)ÈP(1)
C(50)ÈPt(1)ÈP(1)
N(14)ÈPt(1)ÈS(2)
C(50)ÈPt(1)ÈN(14)
175.41(7)
112.75(10)
120.5(3)
135.5(4)
119.1(4)
82.6(2)
84.3(2)
92.9(3)
100.2(2)
176.8(3)
167.80(6)
108.18(9)
119.4(3)
132.3(4)
119.7(3)
Pd(1)ÈN(26)
Pd(1)ÈO(2)
Pd(1)ÈP(3)
Pd(1)ÈS(1)
2.003(5)
2.096(4)
2.220(2)
2.350(2)
S(1)ÈP(1)
P(1)ÈN(1)
N(1)ÈP(2)
P(2)ÈO(2)
2.027(2)
1.598(5)
1.602(5)
1.502(4)
N(26)ÈPd(1)ÈO(2)
N(26)ÈPd(1)ÈP(3)
O(2)ÈPd(1)ÈP(3)
N(26)ÈPd(1)ÈS(1)
O(2)ÈPd(1)ÈS(1)
P(3)ÈPd(1)ÈS(1)
86.1(2)
83.4(2)
169.42(12)
172.5(2)
97.52(12)
93.06(5)
Pd(1)ÈS(1)ÈP(1)
S(1)ÈP(1)ÈN(1)
P(1)ÈN(1)ÈP(2)
N(1)ÈP(2)ÈO(2)
P(2)ÈO(2)ÈPd(1)
104.56(7)
118.3(2)
127.8(3)
117.7(2)
128.4(2)
New J. Chem., 1999, 23, 777È783
781

View Article Online
d(P ) was typically observed around d 12 suggesting the
O
absence of any phosphoryl interaction with the metal centre
whereas d(P ) were indicative of E-monodentate co-ordination
E
modes. Furthermore in the 1H NMR spectrum of 13 and 14
the amine resonance is similar to that observed in
[AuCl(Ph PC H NH )] [d(H) 4.4] consistent with only P-
2
6
4
2
ligation of the hybrid ligand. The absence of l
at 327 cm~1
AuCl
for [AuCl(Ph PC H NH )] and 329 cm~1 for [AuCl(PPh )]
provides further strong evidence for the formation of the
metathesised compounds 11È14.
2
6
4
2
3
The molecular structure of 13 (Fig. 4a, Table 6) shows the
gold(I) centre to be co-ordinated by the PIII donor atom of
Ph PC H NH
and the
S
donor atom of [Ph P-
2
6
4
2
2
(O)NP(S)Ph ]~ in a slightly distorted linear geometry [P(1)È
2
Au(1)ÈS(2) 167.80(6)¡]. The Au(1)ÈP(1) distance [2.286(2) A] is
slightly longer than that in [Au(Ph PC H NH )(C H S)]-
2
6
4
2
4 8
ClO [2.261(2) A]11b and [AuI(Ph PC H NH )] [2.260(4)
4
2
6
4
2
A].11d The Au(1)ÈS(2) distance [2.319(2) A] in 13 is similar
to that in [Au(HL)MPh P(O)NP(S)Ph -SN] [HL \
2
2
Ph PNHP(O)Ph ] [2.335(3) A].1e Within the S(2)ÈP(2)ÈN(2)È
2
2
P(3)ÈO(3) backbone, the bond lengths and angles reÑect some
degree of delocalisation. The P(2)ÈN(2)ÈP(3) angle in 13
[132.3(4)¡]
is
comparable
to
that
reported
in
[Au(HL)MPh P(O)NP(S)Ph -SN] [134.8(6)¡].1e The non-co-
2
2
ordinated amine group is involved in intermolecular hydrogen
bonding (Fig. 4b) linking molecules of 13 into one-
dimensional chains [N(14)É É ÉO(3A) 3.04 A, H(14)É É ÉO(3A) 2.09
A, N(14)ÈH(14)É É ÉO(3A) 163¡].
Conclusion
It has been demonstrated that [Ph P(O)NP(E)Ph ]~ forms a
2
2
variety of mixed PdII, PtII and AuI complexes containing
Ph PC H NH
(or PPh ) ligands. Furthermore [Pt-
(CH )MPh P(O)NP(E)Ph -EN(Ph PC H NH -P,N)]
or Se) are the Ðrst examples of organometallic complexes with
2
6
4
2
2
3
(E \ S
3
2
2
6
4
2
E-monodentate [Ph P(O)NP(E)Ph ]~ ligands.
2
2
Fig. 4 Crystal
structure
of
(a)
[AuMPh P(O)NP(S)Ph -
2
2
SN(Ph PC H NH )] 13 (CÈH hydrogen atoms omitted for clarity), (b)
Acknowledgements
2
6
4
2
intermolecular hydrogen bonding in 13.
We should like to thank Dr S. M. Aucott for a kind donation
of (2-diphenylphosphino)aniline and the EPSRC Mass
Spectrometery Service Centre at Swansea.
chelating Ph PC H NH ligand. The Pt(1)ÈP(1) distance of
2.197(2) A in 7 is similar to that in [PtCl (Ph PC H NH -
2
6
4
2
References
2
2
6
4
2
P,N)][2.188(1) A] whereas the Pt(1)ÈN(14) distance of 2.153(6)
A is longer than that in [PtCl (Ph PC H NH -P,N)][2.048(4)
1 For recent selected examples see: (a) S. W. Magennis, S. Parsons,
A. Corval, J. D. Woollins and Z. Pikramenou, Chem. Commun.,
1999, 61; (b) M. Arca, A. Garau, F. A. Devillanova, F. Isaia, V.
Lippolis, G. Verani, G. L. Abbati and A. Cornia, Z. Anorg. Allg.
Chem., 1999, 625, 517; (c) D. C. Cupertino, R. W. Keyte, A. M. Z.
Slawin and J. D. Woollins, Polyhedron, 1998, 18, 311; (d) P. Bhat-
tacharyya, A. M. Z. Slawin and M. B. Smith, J. Chem. Soc., Dalton
T rans., 1998, 2467; (e) A. M. Z. Slawin, M. B. Smith and J. D.
Woollins, J. Chem. Soc., Dalton T rans., 1998, 1537; ( f ) A. M. Z.
Slawin, M. B. Smith and J. D. Woollins, Polyhedron, 1998, 17,
4465.
2
2
6
4
2
A] reÑecting the di†erence in trans inÑuence of a methyl vs.
chloride ligand.17 The [Ph P(O)NP(S)Ph ]~ anion is bound
2
2
through the soft S-donor atom as would be anticipated on the
basis of the hardÈsoft acidÈbase (HSAB) principle whereas the
““danglingÏÏ PO group is involved in intramolecular H-
bonding with the neighbouring amino NÈH proton
[N(14)É É ÉO(3) 2.73, H(14)É É ÉO(3) 1.77 A, N(14)ÈH(14)É É ÉO(3)
171¡]. Examples of metal complexes with an E-monodentate
[Ph P(O)NP(E)Ph ]~ ligand are conÐned to [Pd(en)-
2 J. E. Drake, A. Silvestru, J. Yang and I. Haiduc, Inorg. Chim. Acta,
1998, 271, 75.
2
2
MPh P(O)NP(E)Ph -EN ] and [AuMPh PNHP(O)Ph NMPh -
3 J. Yang, J. E. Drake, S. Hernandez-Ortega, R. Rosler and C. Sil-
vestru, Polyhedron, 1997, 16, 4061.
2
2
2
2
2
2
P(O)NP(E)Ph -EN] (E \ S or Se).1e
2
The chloride substitution reaction of [AuCl(L)] (L \ PPh
4 A. M. Z. Slawin, M. B. Smith and J. D. Woollins, J. Chem. Soc.,
Dalton T rans., 1996, 3659.
3
or Ph PC H NH ) with one equivalent of I (or II) in meth-
2
6
4
2
5 V. Garcia-Montalvo, R. Cea-Olivares and G. Espinosa-Perez,
Polyhedron, 1996, 15, 829.
6 R. Rosler, J. E. Drake, C. Silvestru, J. Yang and I. Haiduc, J.
Chem. Soc., Dalton T rans., 1996, 391.
anol at room temperature a†ords the white solids
[AuMPh P(O)NP(E)Ph -EN(L)] [E \ S, L \ PPh 11; E \ Se,
2
2
3
L \ PPh 12; E \ S, L \ Ph PC H NH 13; E \ Se, L \
3
2
6
4
2
Ph PC H NH 14] in high yields (69È93%). The composition
7 L. Barkaoui, M. Charrouf, M.-N. Rager, B. Denise, N. Platzer and
H. Rudler, Bull. Soc. Chim. Fr., 1997, 134, 167.
2
6
4
2
of 11È14 was readily conÐrmed by spectroscopic and micro-
analytical data. The 31P-M1HN NMR spectra are in agreement
with the proposed structures for 11È14 with resonances for the
co-ordinated tertiary phosphine at d(P) ca. 37 (for 11 and 12)
and ca. 25 (for 13 and 14). In all cases there is a small down-
Ðeld shift of ca. 5 ppm with respect to d(P) for [AuCl(L)] [d
33.4 (L \ PPh ); 21.0 (L \ Ph PC H NH )]. In addition
8 O. Navratil, E. Herrmann, G. Grossmann and J. Teply, Collect.
Czech. Chem. Commun., 1990, 55, 364.
9 H. Rudler, B. Denise, J. R. Gregorio and J. Vaissermann, Chem.
Commun., 1997, 2299.
10 K. J. Cavell, Aust. J. Chem., 1994, 47, 769.
11 (a) L. Crociani, F. Tisato, F. Refosco, G. Bandoli and B. Corain,
Eur. J. Inorg. Chem., 1998, 1689; (b) J. M. Lopez-de-Luzuriaga, A.
3
2
6
4
2
782
New J. Chem., 1999, 23, 777È783

View Article Online
Schier and H. Schmidbaur, Chem. Ber., 1997, 130, 647; (c) S. Chat-
terjee, D. C. R. Hockless, G. Salem and P. Waring, J. Chem. Soc.,
Dalton T rans., 1997, 3889; (d) P. Papathanasiou, G. Salem, P.
Waring and A. C. Willis, J. Chem. Soc., Dalton T rans., 1997, 3435;
(e) L. Dahlenburg and K. Herbst, Chem. Ber., 1997, 130, 1693; ( f )
M. T. Ahmet, B. Coutinho, J. R. Dilworth, J. R. Miller, S. J.
Parrott, Y. Zheng, M. Harman, M. B. Hursthouse and A. Malik,
J. Chem. Soc., Dalton T rans., 1995, 3041; (g) F. Refosco, F. Tisato,
A. Moresco and G. Bandoli, J. Chem. Soc., Dalton T rans., 1995,
3475; (h) E. W. Ainscough, A. M. Brodie, S. L. Ingham and J. M.
Waters, J. Organomet. Chem., 1994, 468, 229; (i) E. W. Ainscough,
A. M. Brodie, S. L. Ingham and J. M. Waters, Inorg. Chim. Acta,
1994, 217, 191; ( j) M. K. Cooper, P. A. Duckworth, T. W.
Hambley, G. J. Organ, K. Henrick, M. McPartlin and A. Parekh,
J. Chem. Soc., Dalton T rans., 1989, 1067; (k) G. J. Organ, M. K.
Cooper, K. Henrick and M. McPartlin, J. Chem. Soc., Dalton
T rans., 1984, 2377; (l) M. K. Cooper, J. M. Downes, H. J.
Goodwin, M. McPartlin and J. M. Rosalky, Inorg. Chim. Acta,
1983, 76, L155; (m) M. K. Cooper, J. M. Downes, H. J. Goodwin
and M. McPartlin, Inorg. Chim. Acta, 1983, 76, L157; (n) M. K.
Cooper and J. M. Downes, Inorg. Chem., 1978, 17, 880.
13 (a) Siemens SHELXTL, Revision 5.03, Siemens Analytical X-ray
Instruments Inc., Madison, WI, 1995; (b) G. M. Sheldrick,
SADABS, University of Gottingen, 1997.
14 (a) D. J. Williams, A. M. Z. Slawin, J. R. Phillips and J. D. Wool-
lins, Polyhedron, 1996, 15, 3175; (b) P. Bhattacharyya, A. M. Z.
Slawin, D. J. Williams and J. D. Woollins, J. Chem. Soc., Dalton
T rans., 1995, 2489; (c) J. R. Phillips, A. M. Z. Slawin, A. J. P.
White, D. J. Williams and J. D. Woollins, J. Chem. Soc., Dalton
T rans., 1995, 2467.
15 P. Bhattacharyya, J. Novosad, J. Phillips, A. M. Z. Slawin, D. J.
Williams and J. D. Woollins, J. Chem. Soc., Dalton T rans., 1995,
1607.
16 (a) A. Silvestru, I. Haiduc, R. A. Toscano and H. J. Breunig, Poly-
hedron, 1995, 14, 2047; (b) I. Haiduc, R. Cea-Olivares, S.
Hernandez-Ortega and C. Silvestru, Polyhedron, 1995, 14, 2041; (c)
A. M. Z. Slawin, J. Ward, D. J. Williams and J. D. Woollins, J.
Chem. Soc., Chem. Commun., 1994, 421; (d) R. Cea-Olivares and H.
Noth, Z. Naturforsch., T eil. B, 1987, 42, 1507.
17 G. B. Deacon, P. A. Jackson, K. T. Nelson and E. R. T. Tiekink,
Acta Crystallogr., Sect. C, 1991, 47, 2090.
12 SAINT (Siemens Area Detector INTegration) program, Siemens
Analytical X-ray Instruments Inc., Madison, WI, 1995.
Paper 9/02738F
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