Molybdenum(0), ruthenium(II), palladium(II), platinum(II), copper(I) and gold(I) complexes of a new methoxy functionalised bis(phosphino)amine: Synthesis and structure

Article abstract of DOI:10.1039/b001458n

The synthesis, and characterisation, of a new functionalised bis(phosphino)amine Ph₂PN(o-C₆H₄OMe)PPh₂ 1 from o-H₂NC₆H₄OMe and 2 equiv. of Ph₂PCl in diethyl ether at 0

Full text of DOI:10.1039/b001458n

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Molybdenum(0), ruthenium(II), palladium(II), platinum(II), copper(I)
and gold(I) complexes of a new methoxy functionalised
bis(phosphino)amine: synthesis and structure
Kirsty G. Gaw,a Martin B. Smith*a and Alexandra M. Z. Slawinb
a Department of Chemistry, L oughborough University, L oughborough, L eics, UK L E11 3T U.
E-mail: m.b.smith=lboro.ac.uk
b School of Chemistry, University of St. Andrews, St Andrews, Fife, UK KY 16 9ST
Received (in Cambridge, UK) 22nd February 2000, Accepted 21st March 2000
Published on the Web 22nd May 2000
The synthesis, and characterisation, of a new functionalised bis(phosphino)amine Ph PN(o-C H OMe)PPh 1 from
2
6
4
2
o-H NC H OMe and 2 equiv. of Ph PCl in diethyl ether at 0 ¡C is reported. Oxidation of 1 with either aqueous
2
6
4
2
H O , elemental S or grey Se a†ords the phosphorus(V) compounds Ph P(E)N(o-C H OMe)P(E)Ph (E \ O 2; S
2
2
8
2
6
4
2
2
3 or Se 4). Partial oxidation of 1 with 1 equiv. of S in n-hexane a†ords the mixed P(III)/P(V) species Ph P(S)N(o-
8
C H OMe)PPh 5 in addition to small amounts of 3. Reaction of 1 (or 5) with [MX (cod)] (M \ Pd, Pt; X \ Cl or
6
4
2
2
2
CH ; cod \ cycloocta-1,5-diene) a†ords either cis-[MX MPh PN(o-C H OMe)PPh N] (M \ Pd, X \ Cl 6;
3
2
2
6
4
M \ Pt, X \ Cl 7; M \ Pt, X \ CH 8) or the neutral Ðve-membered chelate complexes [MCl MPh P(S)N(o-
3
2
2
C H OMe)PPh N] (M \ Pd 9, M \ Pt 10) in which P,P- or P,S-chelation respectively was observed. Likewise
6
4
2
reaction of [Mo(CO) (nbd)] (nbd \ norbornadiene) or [Cu(MeCN) ]PF with 1 gave cis-[Mo(CO) MPh PN(o-
4
4
6
4
2
C H OMe)PPh N] 11 or [CuMPh PN(o-C H OMe)PPh N ]PF 12. Chloro-bridge cleavage and arene elimination
2 2
of [MRuCl (p-cym)N ] (p-cym \ p-cymene) with 1 (1 : 2 metal : ligand ratio) a†ords, in good yield, the octahedral
6
4
2
2
6
4
6
2
2
bis chelate ruthenium(II) complex trans-[RuCl MPh PN(o-C H OMe)PPh N ] 13. In contrast, reaction of 1 with
2
2
6
4
2 2
two equiv. of [AuCl(tht)] (tht \ tetrahydrothiophene) gave the dinuclear complex [(ClAu)Ph PN(o-
2
C H OMe)PPh (AuCl)] 14 in which the bis(phosphino)amine P,P-bridges two MAuClN metal fragments. All new
6
4
2
compounds have been characterised by a combination of multinuclear NMR [1H, 31PM1HN and 195PtM1HN], IR
spectroscopy and elemental analyses. The molecular structures of six representative examples have been determined
by single-crystal X-ray crystallography.
upon co-ordination, as hemilabile ligands in which the PIII
centre is Ðrmly anchored to the metal whilst there exists a
Introduction
There is immense interest in the development of new
phosphorus(III) ligands for various applications principally
those of homogeneous metal-catalysed reactions. Functional-
isation of for example, tertiary phosphines1 and to a consider-
ably lesser extent, tertiary phosphites2 can provide an
excellent strategy for Ðnely regulating stereoelectronic proper-
ties. Moreover the incorporation of highly polar functional
groups3 or Ñuorous ““ponytailsÏÏ4 into a phosphorus(III) ligand
structure can dramatically increase the solubility of the
resulting ligands and their corresponding complexes in
aqueous and Ñuorous solvents respectively. We have initiated
a programme directed towards the functionalisation of phos-
weak MÈO interaction which can readily be cleaved by sub-
strates e.g. in a homogeneous catalytic reaction.10
Herein we describe the synthesis of a new methoxy func-
tionalised bis(phosphino)amine and present some of its co-
ordination chemistry with selected transition-metals. The
structures of all new compounds have been elucidated by a
combination of multinuclear NMR spectroscopy, IR spectros-
copy, elemental analyses and, in several instances, by X-ray
crystallography.
Experimental
phinoamines, R PN(H)R@ and recently described the facile
General
2
synthesis of two new ligands bearing an ortho keto group
located on the secondary amine R@ moiety.5 Furthermore
All reactions were performed under nitrogen unless otherwise
platinum(II) and rhodium(III) complexes of these ligands were
stated. The starting materials [MC1 (cod)] (M \ Pd, Pt),11,12
2
shown to undergo smooth intramolecular C ÈH bond acti-
[Pt(CH ) (cod)],13 [AuCl(tht)],14 [MRu(p-cym)Cl N ] (p-
sp2
3 2
2 2
vation a†ording extremely rare examples of Ðve-membered
cym \ p-cymene)15 and [RuCl (dmso) ]16 were prepared
2 4
MÈPÈNÈCÈC metallacycles.5 A longer ongoing aim of our
work is modiÐcation of the exocyclic R groups bound to
phosphorus. In contrast the chemistry of ““short-biteÏÏ ligands6
including bis(phosphino)amines7,8 has been reasonably well
documented although pendant O-donor functionalised deriv-
atives remain sparse. The inclusion of ether groups into ter-
tiary phosphines is one popular choice as illustrated by
several very recent reports.9 Particular interest in these
systems originates from the observation that they can behave,
according to previous reported procedures. The compounds
o-H NC H OMe,
Ph PCl,
[Mo(CO) (nbd)]
and
2
6
4
2
4
[Cu(MeCN) ]PF were purchased from Aldrich Chemical Co
4
6
and used directly, with the exception of o-H NC H OMe and
2
6 4
Ph PCl which were distilled prior to use.
2
Infrared spectra were recorded as KBr pellets in the range
4000È220 cm~1 on a Perkin-Elmer System 2000 Fourier-
transform spectrometer. 1H NMR spectra (250 MHz) were
recorded on a Bruker AC250 FT spectrometer with chemical
DOI: 10.1039/b001458n
New J. Chem., 2000, 24, 429È435
429
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shifts (d) in ppm to high frequency of SiMe and coupling
[Pt(CH ) {Ph PN(o-C H OMe)PPh } ], 8. To a solution
4
3 2
3 2
2
6
4
2
constants (J) in Hz, 31PM1HN NMR spectra (36.2 MHz) were
of [Pt(CH ) (cod)] (0.050 g, 0.150 mmol) in toluene (10 cm3)
recorded on a JEOL FX90Q spectrometer with chemical
was added 1 (0.068 g, 0.138 mmol) and the solution stirred for
shifts (d) in ppm to high frequency of 85% H PO and coup-
10 min. The volume was concentrated to ca. 1È2 cm3 by
evaporation under reduced pressure and addition of diethyl
ether (10 cm3) and light petroleum (bp 60È80 ¡C, 10 cm3) gave
a white solid 8. The product was collected by suction Ðltration
and dried in vacuo. Yield: 0.086 g, 80%. Selected IR: 2837
3
4
ling constants (J) in Hz and 195PtM1HN NMR spectra (53.7
MHz) were recorded on a Bruker AC250 FT NMR spectro-
meter with d referenced to external H PtCl (in D O/HCl).
2
6
2
All spectra were measured in CDCl unless otherwise stated.
3
Elemental analyses (Perkin-Elmer 2400 CHN Elemental
l (OMe) cm~1.
CH
Analyzer) were performed by the Loughborough University
Analytical Service within the Department of Chemistry.
Precious metal salts were provided on loan by Johnson
Matthey plc.
[PtCl {Ph P(S)N(o-C H OMe)PPh } ], 10. To the solids 5
2
2
6
4
2
(0.100 g, 0.191 mmol) and [PtCl (cod)] (0.064 g, 0.171 mmol)
2
was added CH Cl (20 cm3). After stirring for 30 min the
2
2
volume was concentrated to ca. 1 cm3 and diethyl ether (20
cm3) added. The pale yellow solid was collected by suction
Ðltration and dried in vacuo. Yield: 0.132 g, 97%. Selected IR:
Preparations
2838 l (OMe); 328, 300 l
cm~1. Slow di†usion of diethyl
Ph PN(o-C H OMe)PPh , 1. A solution of Ph PCl (5.02
CH
PtCl
2
6
4
2
2
ether into a CDCl /CH Cl solution of 10 over several days
g, 22.8 mmol) in Et O (20 cm3) was added dropwise over 45
3
2 2
2
gave crystals suitable for X-ray crystallography.
min to a solution of o-H NC H OMe (1.40 g, 11.4 mmol) and
2
6 4
In a similar manner [PdCl MPh P(S)N(o-C H OMe)PPh N]
NEt (2.35 g, 23.2 mmol) in Et O (50 cm3) at 0 ¡C. The
2
2
6
4
CH
2
3
2
9 was also prepared (73%). Selected IR: 2834 l (OMe); 316,
resulting white suspension was stirred for 18 h, the solvent
evaporated to dryness and degassed distilled water (100 cm3)
added. The solid was collected by suction Ðltration, washed
with n-hexane (50 cm3), absolute EtOH (2 ] 50 cm3) and
dried in vacuo. Yield: 3.57 g, 64%. Selected IR: 2829
289 l
cm~1.
PdCl
[Mo(CO) {Ph PN(o-C H OMe)PPh } ], 11. To a solution
4
4
2
6
4
2
of [Mo(CO) (nbd)] (0.100 g, 0.333 mmol) in CH Cl (20 cm3)
2 2
was added 1 (0.163 g, 0.332 mmol) and the resulting solution
stirred for ca. 2 h. The solution was Ðltered through a small
Celite pad and the volume concentrated in vacuo to ca. 1È2
cm3. Addition of light petroleum (bp 60È80 ¡C, 20 cm3) gave
11. The mixture was stored at ca. 0 ¡C overnight and the solid
collected by suction Ðltration and dried in vacuo. Yield: 0.235
l
(OMe) cm~1.
CH
Ph P(O)N(o-C H OMe)P(O)Ph , 2. A thf (10 cm3) solu-
2
6
4
2
tion of 1 (0.250 g, 0.509 mmol) and aqueous H O (30% w/w,
2
2
0.1 cm3) was stirred for 18 h. The solution was evaporated to
dryness under reduced pressure to give 2 as a white solid.
g, 89%. Selected IR: 2835 l (OMe); 2021, 1922, 1907, 1863
Yield: 0.170 g, 64%. Selected IR: 2835 l (OMe); 1221, 1210
CH
CH
l
cm~1. Slow di†usion of light petroleum into a CDCl
l
cm~1.
CO
3
PO
solution of 11 over 72 h gave crystals suitable for X-ray crys-
tallography.
Ph P(S)N(o-C H OMe)P(S)Ph , 3. To the solids 1 (0.250
2
6
4
2
g, 0.509 mmol) and S (0.038 g, 1.19 mmol) was added thf (20
[Cu{Ph PN(o-C H OMe)PPh } ]PF , 12. To a solution
8
2
6
4
6
2 2
6
cm3) and this was reÑuxed for ca. 18 h. The volume was con-
of [Cu(CH CN) ]PF (0.071 g, 0.191 mmol) in CH Cl (20
3
4
2 2
centrated in vacuo to ca. 1È2 cm3 and addition of n-hexane (20
cm3) gave 3 as a white solid which was collected by suction
cm3) was added 1 (0.187 g, 0.380 mmol) and the resulting solu-
tion stirred for ca. 2 h. The volume was concentrated in vacuo
to ca. 2 cm3 and addition of diethyl ether (15 cm3) gave 12 as
a white solid. Yield: 0.195 g, 86%. Selected IR: 2836
Ðltration. Yield: 0.262 g, 92%. Selected IR: 2840 l (OMe);
CH
611 l cm~1.
PS
In a similar manner Ph P(Se)N(o-C H OMe)P(Se)Ph
4
l
(OMe) cm~1. Slow di†usion of diethyl ether into a CDCl
2
6
4
2
CH
3
was synthesised from 1 and grey Se. Yield: 0.278 g, 84%.
Selected IR: 2834 l (OMe); 571 l cm~1. Slow di†usion of
light petroleum (bp 60È80 ¡C) into a CDCl /CH Cl solution
solution of 12 over 72 h gave crystals suitable for X-ray crys-
tallography.
CH
PSe
3
2 2
of 4 over 72 h gave crystals suitable for X-ray crystallography.
[RuCl {Ph PN(o-C H OMe)PPh } ], 13. To the solids
2
2
6
4
2 2
[MRu(p-cym)Cl N ] (0.020 g, 0.033 mmol) and 1 (0.064 g, 0.130
2 2
Ph P(S)N(o-C H OMe)PPh , 5. A mixture of 1 (0.250 g,
mmol) was added CDCl (1 cm3) to give an immediate dark
red solution. After stirring for ca. 18 h the dark yellow suspen-
2
6
4
2
3
0.509 mmol) and S (0.016 g, 0.499 mmol) in n-hexane (10 cm3)
8
were reÑuxed for 6 h. After allowing the mixture to cool to
sion was Ðltered, the solid washed with a small portion of
room temperature the white solid was collected by suction Ðl-
tration and dried in vacuo. Examination of the solid by
31PM1HN NMR spectroscopy revealed the major species (ca.
90%) to be 5 in addition to small amounts of the disulÐde 3
(ca. 10%). Selected IR: 2831 l (OMe); 667, 629, 613 l
CDCl (0.5 cm3) and dried in vacuo. Yield: 0.067 g, 89%.
3
Selected IR: 2829 l (OMe) cm~1. Alternatively 13 was pre-
CH
pared in lower yield (33%) from [RuCl (dmso) ] and 2 equiv.
2
4
of 1. Suitable crystals of 13 for X-ray crystallography were
obtained by allowing a CDCl solution of [MRu(p-cym)Cl N ]
CH
PS
3
2 2
cm~1.
and 1 to stand for several days.
[{AuCl} {Ph PN(o-C H OMe)PPh } ], 14. To the solids
[PdCl {Ph PN(o-C H OMe)PPh } ], 6.
A
solution of
2
2
6
4
2
2
2
6
4
2
[AuCl(tht)] (0.030 g, 0.092 mmol) and 1 (0.023 g, 0.047 mmol)
[PdCl (cod)] (0.049 g, 0.172 mmol) and 1 (0.086 g, 0.175
2
was added CDCl (2 cm3). The solution was examined by
mmol) in CH Cl (10 cm3) was stirred for ca. 1.5 h. The
3
2
2
31PM1HN NMR spectroscopy and showed the only phos-
volume was concentrated to ca. 1È2 cm3 by evaporation under
reduced pressure and addition of diethyl ether (20 cm3) gave a
yellow solid 6. The product was collected by suction Ðltration
and dried in vacuo. Yield: 0.110 g, 94%. Selected IR: 312, 288
phorus species to be 14. Addition of diethyl ether (15 cm3)
gave 14 as a white solid. Yield: 0.044 g, 94%. Selected IR:
2835 l (OMe); 326 l
cm~1.
CH
AuCl
l
cm~1. Slow di†usion of diethyl ether into a CH Cl solu-
X-Ray crystallography
PdCl
2 2
tion of 6 over 72 h gave crystals suitable for X-ray crystallog-
raphy.
The crystal structures of compounds 4, 6 and 10È13 were
determined using a Rigaku AFC7S serial di†ractometer with
graphite-monochromated (Cu-Ka) radiation (j \ 1.541 78 A)
In a similar manner [PtCl MPh PN(o-C H OMe)PPh N] 7
2
2
6
CH
4
2
(98%) was prepared. Selected IR: 2835 l (OMe); 313, 291
l
cm~1.
and u-scans or a Bruker SMART di†ractometer with
PtCl
430
New J. Chem., 2000, 24, 429È435

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graphite-monochromated Mo-Ka radiation (j \ 0.710 73 A).
Details of the crystal data collections and reÐnements are
given in Table 1. For the SMART data, intensities were col-
lected 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 SAINT17
program) and for the Rigaku AFC7S data collections by
u-scans over a single quadrant of reciprocal space. All data
were corrected for Lorentz, polarisation and long-term inten-
sity Ñuctuations. Absorption e†ects were corrected on the
basis of multiple equivalent reÑections or by empirical
methods.18
not widely been exploited, in part possibly because of the
associated instability of the PÈN bonds in these ligands. The
synthesis of the new ligand Ph PN(o-C H OMe)PPh
1
2
6
4
2
(Scheme 1) by treatment of commercially available Ph PCl
2
with o-H NC H OMe proceeded smoothly in diethyl ether
2
6 4
and gave, after workup, a white solid in 64% yield. Attempts
to
prepare
the
mono(phosphino)amine Ph PNH(o-
2
C H OMe) using a 1 : 1 stoichiometry, gave under the experi-
6
4
mental conditions used here, only 1 after workup albeit in
reduced yield. We have also successfully used this procedure
for the synthesis of other functionalised ligands and these will
be reported in due course. The 31PM1HN NMR spectrum of 1
showed a single resonance at d(P) 65.6 (Table 2) similar to that
previously observed for the unsubstituted ligand
Ph PN(C H )PPh [d(P) 68.86] indicating marginal chemical
Structures were solved by direct methods and reÐned by full
matrix least squares against
F
(TEXSAN19) or F2
(SHELXTL20) for all data with I [ 2p(I). Standard
SHELXTL weighting scheme was used for 4, 6 and 10È12
whilst in the case of 13 the weighting scheme for the Rigaku/
TEXSAN was as previously reported.21 All non H-atoms in
the structures were reÐned anisotropically including the 1/2
weight CHCl in 6 and 10. The additional 1/2 weight CH Cl
2
6
5
2
shift change as a consequence of introducing an o-methoxy
group. Solutions of 1 in CDCl , prepared under anaerobic
3
conditions, are unstable and decompose gradually over ca.
5
d
to give Ph P(O)N(o-C H OMe)P(O)Ph
2
and
2
6
4
2
Ph P(O)PPh . Other pertinent spectroscopic and analytical
data are given in Tables 2 and 3 and the Experimental section.
3
2
2
2
2
in 6 was reÐned isotropically. The two protons on the 1/2
weight CH Cl in 6 were not located. In 10 the CÈH proton
Oxidation of 1 with either aqueous H O , elemental sulfur
2
2
2 2
on the 1/2 weight CHCl was located. For 13 the CÈH
protons on the two CHCl solvates were located whilst the
CÈH protons on the disordered CH Cl were not. All other
protons were reÐned in idealised geometries with a riding
model. ReÐnements converged to residuals given in Table 1.
All calculations were made with programs of SHELXTL
systems.
or grey selenium gave the corresponding phosphorus(v) deriv-
atives 2È4 whose structures were elucidated by analytical
(Table 3), spectroscopic (Table 2) and furthermore, in the case
of 4, by X-ray crystallography. With the exception of 2 [d(P)
26.0] there is a negligible change in 31P chemical shift upon
oxidation [d(P) 67.9 for 3, d(P) 65.8 for 4] and furthermore, in
the case of 4 there is an associated 1J(PSe) of 783 Hz. We also
found that, using conditions identical to those described
by Cavell and co-workers7 for the synthesis of
Ph P(E)N(Ph)PPh (E \ S or Se), we were able to prepare
3
3
2
2
CCDC reference number 440/180. See http://www.rsc.org/
suppdata/nj/b0/b001458n/ for crystallographic Ðles in .cif
format.
2
2
Ph P(S)N(o-C H OMe)PPh 5. However in our hands we
2
6
4
2
were unable to obtain 5 analytically pure although 31PM1HN
NMR spectroscopy revealed the only other phosphorus con-
taining species present was 3 (in ca. 10% by integration of the
two phosphorus species). This compound was identiÐed by its
Results and discussion
The aminolysis of chlorophosphines is an efficient method for
preparing R PN(H)R@ or (R P) NR@ yet this procedure has
2
2 2
Scheme 1 (i) Ph PCl, Et O; (ii) H O or S or grey Se; (iii) 1 equiv. S ; (iv) [MCl (cod)] (M \ Pd or Pt); (v) [MX (cod)] (M \ Pd or Pt, X \ Cl
2
2
2
2
8
8
2
2
or CH ); (vi) [Mo(CO) (nbd)]; (vii) [Cu(CH CN) ]PF ; (viii) [MRu(p-cym)Cl N ]; (ix) 2 equiv. [AuCl(tht)].
2 2
3
4
3
4
6
New J. Chem., 2000, 24, 429È435
431

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Table 1 Crystallographic data for compounds 4, 6 and 10È13
Compound
4
6
10
11
12
13
Empirical formula
M
C
649.40
H
NOP Se
C
770.92
H
Cl
NOP Pd
C
849.21
H
Cl
NOP PtS
C
699.46
H
MoNO P
C
H
CuF N O P
C
H
N O P Cl Ru
10
31 27
2
2
32 28.50 4.50
2
31.50 27.50 3.50
2
35 27
5
2
62 54
6
2
2
5
65 58
2
2
4
1191.46
1478.68
Crystal system
Orthorhombic
15.7749(3)
18.8326(3)
Monoclinic
11.8731(3)
14.3704(3)
21.5491(5)
Monoclinic
15.0814(6)
9.2086(4)
Monoclinic
9.0732(1)
18.9395(2)
19.2823(1)
Monoclinic
11.1500(2)
30.8735(4)
17.2571(3)
Triclinic
12.587(6)
14.127(5)
11.423(6)
92.14(4)
112.82(4)
111.20(3)
1708(2)
293
a/A
b/A
c/A
a/¡
19.4901(4)
25.0051(9)
b/¡
c/¡
V /A
98.502(1)
98.384(1)
96.862(1)
94.393(1)
Ž
3
5790.2(2)
293(2)
Pbca
8
3636.3(2)
293(2)
3435.6(2)
293(2)
3289.8(1)
293(2)
5923.1(2)
293(2)
T /K
Space group
Z
P2 /c
P2 /c
P2 /c
P2 /c
P1
1a
1
1
1
1
4
4
4
4
k/mm~1
2.689
33 146
6966
[R(int) \ 0.1059]
R1 \ 0.0336,
0.954
22 016
8551
[R(int) \ 0.0374]
R1 \ 0.0559,
4.536
14 656
4931
[R(int) \ 0.0283]
R1 \ 0.0261,
0.538
13 779
4677
[R(int) \ 0.0173]
R1 \ 0.0209,
0.567
35 606
13 891
[R(int) \ 0.0718]
R1 \ 0.0578,
wR2 \ 0.1269
0.757
6314
6016
[R(int) \ 0.020]
R1 \ 0.087,
ReÑections collected
Independent
reÑections
Final R indices
[I [ 2p(I)]
wR2 \ 0.0611
wR2 \ 0.1564
wR2 \ 0.0752
wR2 \ 0.0563
wR2 \ 0.119
a Molecule disposed about a centre of symmetry located on the ruthenium.
Table 2 Selected NMR data for compounds 1È14
Compound
d(P)
d(P )a
J(PSe)
J(PtP)
J(PP)
d(Pt)
d(H)b
E
1
2
65.6
3.82
3.51
3.24
3.20
26.0
67.9
65.8
73.5
3
4
783
5c
6
53.7
37.9
22.6
52.0
78.6
73.4
92.4
89.1g
77.7h
84.9
103.5
2.85
2.82
2.69e
2.70
2.72
2.51
2.68
2.63
2.96
7
3343
1607
[4082d
[4170d
8
9
105.7
73.4
61.6
57.0
10
11
12
13
14
3884, 110f
a E \ O, S or Se. b OCH resonance. c Sample also contained small amounts of 3. d 1 : 2 : 1 triplet. e PtÈCH , d 0.80, J(PtH) 73.7, J(PH) 12.8 Hz.
3
3
f 1J(PtP), 2J(PtP) respectively. g u 110 Hz. [PF ]~ counter ion centered at d(P) [144. h Measured in CDCl /CH OH.
1@2
6
3
3
31PM1HN NMR spectrum which showed two well separated
doublets at d(P) 53.7 (PIII) and 73.5 (PV) with a 2J(PP) of ca.
104 Hz.
The molybdenum(0) complex 11 was prepared in a similar
manner by displacement of nbd from [Mo(CO) (nbd)]
4
(nbd \ norbornadiene) with 1 equiv. of 1. In the complexes
The co-ordination chemistry of 1 with various transition-
metal centres has been explored (Scheme 1). Hence reaction of
1 (or 5) with [MX (cod)] (M \ Pd, Pt; X \ Cl, CH ;
6È8 an upÐeld shift in d(P) of between 10 and 40 ppm
was observed whereas for 11, a downÐeld shift in d(P) of ca. 25
ppm was noted (Table 2). In the 1H NMR spectra of 6È11 the
2
3
cod \ cycloocta-1,5-diene) in CH Cl gave the corresponding
OCH group was shifted to lower Ðeld by ca. 1 ppm with
2
2
3
metal(II) complexes 6È10 in good to high yields (ca. 90%).
respect to the free ligand 1. The isolated dichlorometal(II)
complexes 6 and 7 have a cis conÐguration since two distinct
MÈCl stretches were observed in their IR spectra. For 11 four
strong carbonyl absorptions in the region 2021È1863 cm~1
are characteristic of a Group 6 cis tetracarbonyl metal
complex. Reaction of two equiv. of 1 with [Cu(CH CN) ]PF
Table 3 Microanalytical dataa for compounds 1È4 and 6È14
Analysis (%)
3
4
6
in CH Cl
gave the d10 cationic copper complex
2
2
Compound
C
H
N
[CuMPh PN(o-C H OMe)PPh N ]PF 12 whereas reaction of
2
6
4
2 2
6
1 with [MRu(p-cym)Cl N ] gave the octahedral ruthenium(II)
1
2
75.50(75.80)
70.80(71.10)
66.40(67.00)
57.10(57.30)
56.20(55.70)
49.45(49.20)
55.00(55.30)
52.60(53.10)
44.70(44.55)
60.50(60.10)
62.10(62.50)
63.75(64.45)
38.45(38.95)
5.50(5.50)
5.10(5.20)
4.75(4.90)
4.10(4.20)
4.20(4.10)
3.60(3.60)
4.55(4.65)
3.85(3.90)
3.25(3.25)
4.25(3.90)
4.90(4.60)
4.60(4.70)
2.70(2.85)
2.05(2.80)
2.60(2.70)
2.45(2.50)
1.85(2.20)
1.90(2.10)
1.75(1.80)
1.90(1.95)
1.60(2.00)
1.45(1.65)
1.75(2.00)
2.70(2.40)
2.40(2.45)
1.35(1.45)
2 2
complex [RuCl MPh PN(o-C H OMe)PPh N ] 13. Indepen-
2
2
6
4
2 2
dently we also prepared 13 from [RuCl (dmso) ] and 2 equiv.
3
2
4
of 1 albeit in reduced yield (33%). The trans isomer of 13 was
isolated as indicated by one singlet in the 31P NMR spectrum
at d(P) 77.7. In contrast we Ðnd that when 1 was reacted with
the d10 starting material [AuCl(tht)] (tht \ tetrahydrothio-
phene) the binuclear species 14 was obtained in 94% yield.
Here 1 bridges two MAuClN metal fragments. The downÐeld
shift [d(P) 84.9] and the observation of one AuÈCl stretch at
326 cm~1 in the infrared spectrum were in accord with com-
4
6
7
8
9
10b
11
12
13
14
plexation of 1. Ligands of this PÈNÈP class [i.e. RN(PX ) ,
R \ alkyl; X \ alkoxy, F] have previously been used in the
2 2
a Calculated values in parentheses. b Contains 0.5CHCl as solvate.
3
preparation of heterobimetallic complexes.22 Jones et al.
432
New J. Chem., 2000, 24, 429È435

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Fig. 1 Crystal structure of 4.
Fig. 3 Crystal structure of 11.
Table 6 Selected bond distances (A) and angles (¡) for compound 11
Table 4 Selected bond distances (A) and angles (¡) for compound 4
P(1)ÈSe(1)
2.1056(6)
2.0936(7)
116.08(6)
124.77(10)
P(1)ÈN(1)
1.727(2)
1.725(2)
114.80(7)
P(2)ÈSe(2)
N(1)ÈP(2)
Mo(1)ÈP(1)
2.5102(5)
2.4880(5)
1.998(2)È2.045(2)
P(1)ÈN(1)
N(1)ÈP(2)
1.729(2)
1.729(2)
Se(1)ÈP(1)ÈN(1)
P(1)ÈN(1)ÈP(2)
N(1)ÈP(2)ÈSe(2)
Mo(1)ÈP(2)
Mo(1)ÈC range
Mo(1)ÈP(1)ÈN(1) 94.49(5)
Mo(1)ÈP(2)ÈN(1) 95.29(5)
P(1)ÈMo(1)ÈP(2)
P(1)ÈN(1)ÈP(2)
65.78(2)
103.43(8)
recently described some unusual dinuclear gold(I) and gold(III)
complexes with bidentate 1,2-MPh PN(H)N C H and 3,4-
2
2 6 4
MPh PN(H)N MeC H ligands.23
2
2
6 3
[124.77(10)¡] is smaller than that found in MPh P(Se)N NH
The crystal structure of 4 (Fig. 1, Table 4) is broadly as
anticipated. The P2Se bond lengths [2.1056(6) and 2.0936(7)
A] are similar to those observed for MPh P(Se)N NH [2.085(1)
2
2
[132.3(2)¡].24
The crystal structure of 6 (Fig. 2, Table 5) entails a cis dis-
posed Ph PN(o-C H OMe)PPh and two chloride ligands
around a palladium centre. The geometry is best described as
distorted square-planar as reÑected by the bond angles [P(1)È
Pd(1)ÈP(2) 71.99(5), P(2)ÈPd(1)ÈCl(2) 94.73(6), Cl(1)ÈPd(1)È
Cl(2) 96.36(6), P(1)ÈPd(1)ÈCl(1) 96.88(5)¡]. The Pd(1) is 0.04 A
2
2
and 2.101(1) A], C H MNHP(Se)Ph N [2.081(6) and 2.107(5)
2
6
4
2
6
4
2 2
A] and MPh P(Se)NPPh N [2.120(2) and 2.122(2) A].24h26
2
2 2
Furthermore the PÈN bond lengths [1.727(2) and 1.725(2) A]
are marginally longer than those in MPh P(Se)N NH [1.678(4)
2
2
and 1.686(3) A] which exists in the solid state as a NÈHÉ É ÉSe
hydrogen bonded dimer pair.24 The PÈNÈP angle
below the plane of its four substituents and the PdP N ring is
2
essentially planar. The PdÈCl and PdÈP bond lengths are all
normal27,28 whilst the PÈN distances [1.701(4) and 1.714(4)
A] may indicate some partial double bond character. As a
consequence of P,P-chelation the P(1)ÈN(1)ÈP(2) angle is
99.3(2)¡ but in contrast, when R PN(R)PR ligands span two
2
2
metal centres, as in [Pd Cl MPhNMP(OPh) N N ] and
2 2 2
2
2
[Pd MMeNMP(OPh) N N ], the PÈNÈP angle is enlarged and
falls in the range 113È120¡.29 There is no Pd(1)É É ÉO(26) inter-
2
2 2 3
action (5.3 A).
The crystal structure of 11 (Fig. 3, Table 6) shows that the
geometry around the molybdenum is distorted octahedral
with a cis chelating Ph PN(o-C H OMe)PPh ligand and
2
6
4
2
four terminal carbon monoxide ligands. The four-membered
Fig. 2 Crystal structure of 6 (solvent molecules omitted for clarity).
Table 5 Selected bond distances (A) and angles (¡) for compound 6
Pd(1)ÈCl(1)
2.369(2)
2.353(2)
2.2196(13)
96.36(6)
96.88(5)
168.87(6)
94.73(6)
166.46(6)
Pd(1)ÈP(2)
2.2078(13)
1.701(4)
1.714(4)
71.99(5)
94.30(14)
99.3(2)
Pd(1)ÈCl(2)
P(1)ÈN(1)
Pd(1)ÈP(1)
N(1)ÈP(2)
Cl(1)ÈPd(1)ÈCl(2)
Cl(1)ÈPd(1)ÈP(1)
Cl(1)ÈPd(1)ÈP(2)
Cl(2)ÈPd(1)ÈP(2)
Cl(2)ÈPd(1)ÈP(1)
P(1)ÈPd(1)ÈP(2)
Pd(1)ÈP(1)ÈN(1)
P(1)ÈN(1)ÈP(2)
N(1)ÈP(2)ÈPd(1)
94.34(14)
Fig. 4 Crystal structure of 12 (PF ~ counter ion omitted for clarity).
6
New J. Chem., 2000, 24, 429È435
433

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Table 7 Selected bond distances (A) and angles (¡) for compound 12
Table 9 Selected bond distances (A) and angles (¡) for compound 10
Cu(1)ÈP(1)
2.3010(12)
2.3268(12)
2.2944(12)
2.3330(12)
73.19(4)
132.12(5)
132.18(5)
130.06(5)
126.16(5)
73.06(4)
P(1)ÈN(1)
1.719(3)
1.717(3)
1.705(3)
1.720(3)
90.21(11)
89.41(11)
90.75(12)
89.08(12)
106.8(2)
107.1(2)
Pt(1)ÈCl(1)
2.3515(12)
2.3164(13)
2.2948(12)
2.2029(12)
89.76(5)
88.46(5)
178.73(5)
89.20(4)
S(1)ÈP(1)
P(1)ÈN(1)
N(1)ÈP(2)
2.010(2)
1.688(4)
1.735(4)
Cu(1)ÈP(2)
N(1)ÈP(2)
Pt(1)ÈCl(2)
Cu(1)ÈP(3)
Cu(1)ÈP(4)
P(3)ÈN(3)
N(3)ÈP(4)
Pt(1)ÈS(1)
Pt(1)ÈP(2)
Cl(1)ÈPt(1)ÈCl(2)
Cl(1)ÈPt(1)ÈS(1)
Cl(1)ÈPt(1)ÈP(2)
Cl(2)ÈPt(1)ÈP(2)
Cl(2)ÈPt(1)ÈS(1)
P(1)ÈCu(1)ÈP(2)
P(1)ÈCu(1)ÈP(3)
P(1)ÈCu(1)ÈP(4)
P(2)ÈCu(1)ÈP(3)
P(2)ÈCu(1)ÈP(4)
P(3)ÈCu(1)ÈP(4)
Cu(1)ÈP(1)ÈN(1)
Cu(1)ÈP(2)ÈN(1)
Cu(1)ÈP(3)ÈN(3)
Cu(1)ÈP(4)ÈN(3)
P(1)ÈN(1)ÈP(2)
P(3)ÈN(3)ÈP(4)
P(2)ÈPt(1)ÈS(1)
Pt(1)ÈS(1)ÈP(1)
S(1)ÈP(1)ÈN(1)
P(1)ÈN(1)ÈP(2)
N(1)ÈP(2)ÈPt(1)
92.53(14)
97.43(6)
108.52(14)
116.2(2)
175.45(4)
108.70(13)
2.4880(5) A] in 11 are slightly longer than found in
[Mo(CO) MPhNP(OC H ) N ] [MoÈP 2.440(2), 2.427(2) A]
MoP N ring is essentially planar and the MoÈP/PÈN dis-
2
4
6 5 2 2
poorer p-acceptor ligand than
tances compare well with those of [Mo (CO) Ml-cis-
indicating
1
is
a
2
8
[PhNP(OC H Me-p)] N ] [MoÈP 2.484(2), 2.476(2) A; PÈN
PhNMP(OC H ) N .32 The PÈNÈP angle in 11 [103.43(8)¡]
6
4
2 2
6
5 2 2
range 1.701(4)È1.716(3) A]30 and [Mo(CO) MEtNP(OC H Br-
di†ers by approximately ^3¡ with respect to that found in
complexes 6 and 12.
4
6 4
4)N ] [average MoÈP 2.452(5) A; PÈN ca. 1.70(1) A].31 In con-
3
trast the observed MoÈP bond lengths [2.5102(5) and
The crystal structure of the cationic complex 12 (Fig. 4,
Table 7) conÐrms a markedly distorted tetrahedral geometry
of the copper(I) metal centre with the co-ordination sphere
occupied by two chelating Ph PN(o-C H OMe)PPh ligands.
2
6
4
2
The CuÈP bond distances are normal [2.2944(12)È2.3330(12)
A] whilst the PÈN bond lengths [1.705(3)È1.719(3) A] are
similar to those found in 4. Both CuP N rings are essentially
2
planar and orthogonal to each other. Within both metallo-
rings, the PÈNÈP angles [106.8(2) and 107.1(2)¡] are slightly
enlarged with respect to that found in 11.
The crystal structure of 13 (Fig. 5, Table 8) shows the
ruthenium(II) centre to be essentially octahedral with two
chloride and two Ph PN(o-C H OMe)PPh ligands disposed
2
6
4
2
in a trans conÐguration. Within the four-membered RuP N
2
ring the considerable ring strain is reÑected by an acute P(1)È
Ru(1)ÈP(2) angle of 69.84(9)¡. The RuÈP, RuÈCl and PÈN
distances in 13 are slightly shorter than those in the ruth-
enium(II) complex [Ru(g5-C H )ClM(Ph P) NHN] [2.2777(10),
5
5
2 2
2.2813(10); 2.4607(10) and 1.692(3), 1.694(3) A respectively].33
Within the RuP N metallacycle the PÈNÈP angle of 101.2(4)¡
is somewhat enlarged with respect to that of 6 but contracted
2
Fig. 5 Crystal structure of 13 (solvent molecules omitted for clarity).
Table 8 Selected bond distances (A) and angles (¡) for compound 13
in comparison to 11 and 12.
The crystal structure of 10 (Fig. 6, Table 9) shows a mono-
meric chelated metal complex with a square-planar environ-
ment comprising a central platinum centre, a P,S-bound
Ph P(S)N(o-C H OMe)PPh ligand and a cis disposition of
Ru(1)ÈCl(1)
2.416(3)
2.348(3)
2.2332(2)
88.49(9)
87.89(9)
91.51(9)
92.11(9)
101.2(4)
P(1)ÈN(1)
N(1)ÈP(2)
1.714(7)
1.754(8)
Ru(1)ÈP(1)
2
6
4
2
Ru(1)ÈP(2)
two chloride ligands. The Pt is 0.05 A below the plane of the
four donor substituents. Within the PtÈSÈPÈNÈP Ðve-
membered metallacycle S(1) shows a maximum deviation
[0.33 A] out of the plane. The Pt(1)ÈCl(1) bond length
[2.3515(2) A] is larger than that of Pt(1)ÈCl(2) [2.3164(13) A]
and as anticipated for the di†erent trans inÑuences of phos-
phorus vs. sulfur donor atoms. The PÈS and PÈN bond dis-
tances and angles are comparable to those reported by Cavell
and co-workers for [PtCl MPh P(S)N(Ph)PPh N].7
Cl(1)ÈRu(1)ÈP(1)
Cl(1)ÈRu(1)ÈP(2)
Cl(1)ÈRu(1)ÈP(1A)
Cl(1)ÈRu(1)ÈP(2A)
P(1)ÈN(1)ÈP(2)
P(1)ÈRu(1)ÈP(2)
P(1)ÈRu(1)ÈP(2A)
Ru(1)ÈP(1)ÈN(1)
N(1)ÈP(2)ÈRu(1)
69.84(9)
110.16(9)
94.8(3)
94.2(2)
2
2
2
Conclusion
In conclusion, we have shown the facile synthesis of a new
bis(phosphino)amine and its co-ordination chemistry with a
range of transition-metals. Further studies are in progress and
will be reported in due course.
Acknowledgements
We should like to thank the EPSRC for a studentship
(K.G.G), InÐneum UK Ltd for Ðnancial support, and Johnson
Matthey plc for the generous loan of precious metal salts.
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Fig. 6 Crystal structure of 10 (solvent molecule omitted for clarity).
434
New J. Chem., 2000, 24, 429È435

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435