Synthesis and characterisation of the bidentately attached linear triphos complexes 2-RC2R)> . X-ray crystal structures of 2-PhC2Ph)> (X = Br and I) and <MoI2(O)<Ph2P(CH2)2PPh(CH2)...

Article abstract of DOI:10.1016/S0022-328X(98)01153-X

Reaction of equimolar quantities of 2-RC2R)2> and L in CH2Cl2 at room temperature gives the bidentately coordinated triphos complexes 2-RC2R)> (M = Mo, X = Y = I, R = Me or Ph; M = W, X = Y = Br, R = Me or Ph; M = W, X = Br, Cl, Y = I, R = Me or Ph) (1-8) in high yield. The molecular structures of 2-PhC2Ph)> (X = Br, I) have been determined crystallographically and are equivalent. The coordination geometry about the tungsten atom in both complexes is distorted octahedral with two adjacent phosphorus atoms in the triphos ligand, a halide and a carbonyl ligand occupying the equatorial plane, with the diphenylacetylene and the other halide atom occupying the axial positions. The 13C-NMR spectrum of WBr2(CO)(L-P,P')η²-PhC2Ph (4) shows the diphenylacetylene ligand is donating four electrons to the metal. Refluxing a slightly wet acetonitrile solution of 2-MeC2Me)> for 24 h affords the unusual crystallographically characterised molybdenum(IV) oxidised triphos complex (MoI2(O)> (9). - Keywords: Molybdenum; Tungsten; Alkynes; Triphos; Carbonyls; Halide; Crystal structure; Oxide complex

Full text of DOI:10.1016/S0022-328X(98)01153-X

Journal of Organometallic Chemistry 580 (1999) 265–272
Synthesis and characterisation of the bidentately attached linear
triphos complexes [MXY(CO)(L-P,P%)(h2-RC2R)] {M=Mo, W; X,
Y=Cl, Br, I; L=PhP(CH2CH2PPh2)2; R=Me, Ph}. X-ray crystal
structures of [WX2(CO)(L-P,P%)(h2-PhC2Ph)] (X=Br and I) and
[MoI2(O){Ph2P(CH2)2PPh(CH2)2POPh2-P,P%,O}]
Paul K. Baker a,*, Michael G.B. Drew b, Margaret M. Meehan a, John Szewczyk a
a Department of Chemistry, Uni6ersity of Wales, Bangor, Gwynedd, LL57 2UW, UK
b Department of Chemistry, Uni6ersity of Reading, Whiteknights, Reading, RG6 6AD, UK
Received 20 October 1998
Abstract
Reaction of equimolar quantities of [MXY(CO)(NCMe)(h2-RC2R)2] and L {L=PhP(CH2CH2PPh2)2} in CH2Cl2 at room
temperature gives the bidentately coordinated triphos complexes [MXY(CO)(L-P,P%)(h2-RC2R)] (M=Mo, X=Y=I, R=Me or
Ph; M=W, X=Y=Br, R=Me or Ph; M=W, X=Br, Cl, Y=I, R=Me or Ph) (1–8) in high yield. The molecular structures
of [WX2(CO)(L-P,P%)(h2-PhC2Ph)] (X=Br, I) have been determined crystallographically and are equivalent. The coordination
geometry about the tungsten atom in both complexes is distorted octahedral with two adjacent phosphorus atoms in the triphos
ligand, a halide and a carbonyl ligand occupying the equatorial plane, with the diphenylacetylene and the other halide atom
occupying the axial positions. The 13C-NMR spectrum of WBr2(CO)(L-P,P%)h2-PhC2Ph (4) shows the diphenylacetylene ligand is
donating four electrons to the metal. Refluxing a slightly wet acetonitrile solution of [MoI2(CO)(L-P,P%)(h2-MeC2Me)] for 24 h
affords the unusual crystallographically characterised molybdenum(IV) oxidised triphos complex [MoI2(O){Ph2P(CH2)2PPh-
(CH2)2POPh2-P,P%,O}] (9). © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Molybdenum; Tungsten; Alkynes; Triphos; Carbonyls; Halide; Crystal structure; Oxide complex
1. Introduction
tungsten(II) complexes containing such groups have
been described.
Recently [21], we described the synthesis, molecular
structures (R=Me, R%=Me or Ph) and reactions as
monodentate phosphines with molybdenum(II) and
tungsten(II) complexes, the bidentately attached linear
triphos {linear triphos=PhP(CH2CH2PPh2)2} tungsten
complexes [WI2(CO)(L-P,P%)(h2-RC2R%)] (R=R%=Me
or Ph; R=Me, R%=Ph). In this paper we extend this
work to the preparation of molybdenum complexes and
mixed halide complexes of the type [MXY(CO)(L-
P,P%)(h2-RC2R)] {M =Mo, X=Y=I, R=Me or Ph;
M=W, X=Y=Br, R=Me or Ph; M=W, X=Br or
Cl, Y=I, R=Me or Ph; L=PhP(CH2CH2PPh2)2}.
The X-ray crystal structures of [WX2(CO)(L-P,P%)(h2-
Molybdenum(II) and tungsten(II) haloalkyne com-
plexes have been much studied over the years [1,2],
including phosphine complexes of the type
[MX2(CO)L2(h2-RC2R%)] (M=Mo or W; X=Cl, Br,
I; L=monodentate phosphine, L2=bidentate phos-
phine; R,R%=H, alkyl or aryl) [3–11]. Organotransi-
tion-metal complexes containing pendant phosphine
groups have been prepared and studied to form
bimetallic complexes over the years [12–20]. However,
apart from our work very few molybdenum(II) and
* Corresponding author. Fax: +44-01248-370528.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(98)01153-X

266
P.K. Baker et al. / Journal of Organometallic Chemistry 580 (1999) 265–272
PhC2Ph)] (X=Br, I) are discussed also and the oxida-
tion of [MoI2(CO)(L-P,P%)(h2-MeC2Me)] in refluxing
acetonitrile to give the crystallographically character-
ised complex [MoI2(O){Ph2P(CH2)2PPh(CH2)2POPh2-
P,P%,O}].
metal has little effect on s-donor/p-acceptor properties
of the carbonyl ligand. The complexes 1–8 also have
alkyne (CꢀC) stretching frequencies at considerably
lower wavenumber than for the unattached alkyne.
Single crystals of [WX2(CO)(L-P,P%)(h2-PhC2Ph)]
(X=Br and I) suitable for X-ray crystallography were
grown from concentrated solutions of CH2Cl2/Et2O
(4:1) mixtures at −17°C for several weeks. It should be
noted that the diiodide complex [WI2(CO)(L-P,P%)(h2-
PhC2Ph)] has been prepared previously [21]. The molec-
ular structures of [WBr2(CO)(L-P,P%)(h2-PhC2Ph)] (4)
and [WI2(CO)(L-P,P%)(h2-PhC2Ph)] (10), respectively,
are shown in Figs. 1 and 2 together with the atomic
numbering scheme, and the atomic coordinates and
bond lengths and angles are given in Table 3.
2. Results and discussion
Equimolar quantities of [MXY(CO)(NCMe)(h2-
RC2R)2] [11,22–24] and L {L=PhP(CH2CH2PPh2)2}
react in CH2Cl2 at room temperature to afford eventu-
ally the new complexes [MXY(CO)(L-P,P%)(h2-RC2R)]
(M=Mo, X=Y=I, R=Me or Ph; M=W, X=Y=
Br, R=Me or Ph; M=W, X=Br or Cl, Y=I, R=
Me or Ph) (1–8) via displacement of acetonitrile and an
alkyne ligand. Complexes 1–8 have been characterised
by elemental analysis (C, H and N) (Table 1), IR
The structures of [WX2(CO)(L-P,P%)(h2-PhC2Ph)]
{X=Br (4), X=I(10)} are shown in Figs. 1 and 2,
together with the atomic numbering schemes. The
structures are equivalent but not isomorphous. The
metal atoms can best be considered as occupying a
distorted octahedral environment with the dipheny-
lacetylene ligand occupying one site trans to an iodine.
Dimensions are given in Table 3. Two of the phospho-
rus atoms in the triphos ligand are bonded to the metal,
with P(1) trans to carbonyl giving rise to a longer bond
1
spectroscopy, H-NMR, 31P-NMR spectroscopy (Table
2) and for 4 by 13C-NMR spectroscopy. The complexes
[MoI2(CO)(L-P,P%)(h2-PhC2Ph)] · 0.5CH2Cl2
(2),
[WBrI(CO)(L-P,P%)(h2-MeC2Me)] · CH2Cl2 (5) and
[WClI(CO)(L-P,P%)(h2-PhC2Ph)] · CH2Cl2 (8) were
confirmed as solvates by repeated elemental analyses
and 1H-NMR spectroscopy. Complexes 1–8 are rea-
sonably soluble in chlorinated solvents such as CH2Cl2
and CHCl3; however, they are much less soluble in
diethyl ether and hydrocarbon solvents. As expected,
the 2-butyne complexes are more soluble than their
diphenylacetylene counterparts. All the complexes are
air-sensitive in solution, but can be stored in the solid
state in the absence of air for several days. It appears
that the molybdenum complexes are less stable than
their tungsten counterparts, and the mixed halide com-
plexes less stable than their dihalo counterparts.
˚
˚
(2.589 (4) A) in (4), (2.563 (3) A) in [WI2(CO)(L-
P,P%)(h2-PhC2Ph)] (10) than P(4) trans to iodide
˚
(2.489(4), 2.513 (3) A). This arrangement of atoms in
the metal coordination sphere is equivalent to that
found
for
[WI2(CO)(L-P,P%)(h2-MeC2Ph)]
and
[WI2(CO)(L-P,P%)(h2-MeC2Me)] [21] where the third
phosphorus atom of the triphos is unattached. How-
ever, in [WI2(CO)(dppm)(h2-MeC2Me)], the two phos-
phorus atoms are trans to an iodine and the but-2-yne
[6].
The infrared spectra of complexes 1–8 all show a
single carbonyl band in their spectra in the range
1955–1979 cm−1. Complexes with identical halide
groups and alkyne ligands have similar carbonyl
stretching bands, which suggests that as expected the
In [WI2(CO)(L-P,P%)(h2-PhC2Ph)], the iodine I(3)
trans to the diphenylacetylene forms a longer bond
{2.840(2) A} than the iodine I(2) trans to phosphorus
˚
P(4). This is true also for the W–Br distances in the
complex [WBr2(CO)(L-P,P%)(h2-PhC2Ph)] (4), which
Table 1
Physical and analytical data for the complexes [MXY(CO)(L-P,P%)(h2-RC2R%)] (1–8) and [MoI2(O){Ph2P(CH2)2PPh(CH2)2POPh2-P,P%,O}] (9)a
Complex
Colour
Yield (%)
Analysis (%)
C
H
1
2
3
4
5
6
7
8
9
[MoI2(CO)(L-P,P%)(h2-MeC2Me)]
Brown
Brown
Purple
Blue
Purple
Green
Purple
Green
Dark brown
88
91
85
91
89
79
94
84
80
48.2 (48.5)
52.2 (52.5)
48.5 (48.8)
54.6 (54.3)
43.4 (44.0)
52.3 (52.0)
48.9 (48.6)
51.3 (51.2)
44.9 (44.4)
3.8 (4.1)
3.4 (3.9)
4.0 (4.1)
4.2 (4.0)
3.7 (3.8)
3.8 (3.8)
4.6 (4.1)
4.3 (3.9)
3.9 (3.9)
[MoI2(CO)(L-P,P%)(h2-PhC2Ph)]0.5CH2Cl2
[WBr2(CO)(L-P,P%)(h2-MeC2Me)]
[WBr2(CO)(L-P,P%)(h2-PhC2Ph)]
[WBrI(CO)(L-P,P%)(h2-MeC2Me)].CH2Cl2
[WBrI(CO)(L-P,P%)(h2-PhC2Ph)]
[WClI(CO)(L-P,P%)(h2-MeC2Me)]
[WClI(CO)(L-P,P%)(h2-PhC2Ph)].CH2Cl2
[MoI2(O){Ph2P(CH2)2PPh(CH2)2POPh2-P,P%,O}].0.5CH2Cl2
a Calculated values in parentheses.

P.K. Baker et al. / Journal of Organometallic Chemistry 580 (1999) 265–272
267
Table 2
Infrareda, 1Hb- and 31Pc-NMR spectroscopic data for the complexes [MXY(CO)(L-P,P%)(h2-RC2R)]
Complex (CꢀO) cm−1 (CꢀC) cm−1 1H-NMR data (l) ppm 31P-NMR data (l)
1
2
3
1976 (s)
1979 (s)
1958 (s)
1588(w)
1589 (w)
1656 (w)
7.9–7.4 (m, 25H, Ph); 3.1 (s, 6H, C2Me); 2.6–2.4 37.8 (d, 1P, JP–P=26 Hz, C2H4PPh); 31.4 (d,
(m, 8H, CH2)
1P, JP–P=30 Hz, C2H4PPh); 14.4 (s, 2P,
C2H4PPh2); −13.7 (m, 2P, C2H4PPh2)
7.9–7.4 (m, 35H, Ph); 5.3 (s, 1H, CH2Cl2); 2.5– 34.4 (d, 1P, JP–P=29 Hz, C2H4PPh2); 32.2 (d,
2.2 (m, 8H, CH2)
1P, JP–P=31 Hz, C2H4PPh2); 12.8 (s, 2P,
C2H4PPh2); −13.5 (m, 2P, C2H4PPh2)
7.9–7.4 (m, 25H, Ph); 3.1 (s, 6H, C2Me); 2.6–2.4 32.6 (d, 1P, JP–P=34 Hz, JW–P=282 Hz;
(m, 8H, CH2)
C2H4PPh); 30.1 (d, 1P, JP–P=34 Hz, JW–P=
279 Hz; C2H4PPh); 11.3 (s, 1P, JW–P=279 Hz,
C2H4PPh2); 5.6 (s, 1P, JW–P=280 Hz,
C2H4PPh2); −13.5 (m, 2P, C2H4PPh2)
34.8 (d, 1P, JP–P=30 Hz, JW–P=297 Hz,
4
5
6
7
8
1963 (s)
1958 (s)
1964 (s)
1955 (s)
1963 (s)
1655 (w)
1586(w)
1588 (w)
1657 (w)
1600 (w)
7.9–7.5 (m, 35H, Ph); 2.8–2.6 (m, 8H, CH2)
C2H4PPh); 29.6 (d, 1P, JP–P=37 Hz, JW–P
=
N.O., C2H4PPh); 5.1 (d, 1P, JP–P=36 Hz, JW–P
=295 Hz, C2H4PPh2); −13.6 (m, 2P,
C2H4PPh2)
7.9–7.5 (m, 25H, Ph); 5.3 (s, 2H, CH2Cl2); 3.1,
3.0 (s, 6H, C2Me); 2.4–2.2 (m, 8H, CH2)
31.2 (d, 1P, JP–P=20 Hz, JW–P=N.O.,
C2H4PPh); 11.3 (s, 1P, JW–P=265 Hz,
C2H4PPh); 5.0 (d, 1P, JP–P=30 Hz, JW–P=282
Hz, C2H4PPh2); −2.5 (s, 1P, JW–P=260 Hz,
C2H4PPh2); −13.6 (m, 2P, C2H4PPh2)
33.1 (d, 1P, JP–P=20 Hz, JW–P=N.O.,
C2H4PPh); 26.1 (s, 1P, JW–P=N.O., C2H4PPh);
5.3 (d, 1P, JP-P=21 Hz, JW-P=N.O.,
C2H4PPh2); -4.2 (d, 1P, JP-P=30 Hz,
C2H4PPh2); −13.5 (m, 2P, C2H4PPh2)
7.9–7.6 (m, 35H, Ph); 2.4–2.2 (m, 8H, CH2)
7.9–7.4 (m, 25H, Ph); 3.05, 3.0, 2.95, 2.9 (s, 6H, 35.2 (d, 1P, JP–P=22 Hz, JW–P=N.O.,
C2Me); 2.4–2.2 (m, 8H, CH2)
CH2PPh); 33.6 (d, 1P, JP–P=21 Hz, JW–P
N.O., CH2PPh); 23.4 (s, 1P, JW–P=N.O.,
=
C2H4PPh2); 15.1 (s, 1P, C2H4PPh2); −13.7 (m,
2P, C2H4PPh2)
7.9–7.4 (m, 35H, Ph); 5.3 (s, 2H, CH2Cl2); 2.6– 36.8 (d, 1P, JP–P=22Hz, JW–P=N.O.,
2.4 (m, 8H, CH2) CH2PPh); 35.7 (d, 1P, JP–P=23Hz, JW–P
=
N.O., C2H4PPh); 10.3 (s, 1P, JW–P=N.O.,
C2H4PPh2); 7.9 (s, 1P, JW–P=N.O.,
C2H4PPh2); −13.6 (m, 2P, C2H4PPh2)
a Spectra recorded in CHCl3 as thin films between NaCl plates; s=strong, w=weak
b Spectra recorded in CDCl3 (+25) and referenced to SiMe4, m=multiplet, s=singlet
c Spectra recorded in CD2Cl2 (+25) and referenced to H3PO4; s=singlet, d=doublet, m=multiplet. N.O.=not observed.
In order to elucidate a possible mechanism of the
reaction between quantities of [WI2(CO)(NCMe)(h2-
PhC2Ph)2] and L, the reaction was followed by
31P{1H}-NMR spectroscopy at low temperature. At
0°C the 31P{1H}-NMR spectrum (CDCl3) shows only
resonances due to the uncoordinated linear triphos at
l= −13 ppm (doublet) and −17 ppm (triplet). On
warming the NMR solution to 10°C, the intensity of
both resonances at −13 and −17 ppm decreases and
two new resonances at −35.6 ppm (triplet, JP–P=30
Hz) and −4 ppm (brd) appear. It is likely that the
resonances at l= −35.6 ppm and −4 ppm are due
to the uncoordinated central phosphorus and the
monodentate coordinated phosphorus in the initially
formed intermediate, [WI2(CO)(L-P)(h2-PhC2Ph)2], to-
gether with the resonance at −13 ppm which can be
ascribed to the uncoordinated end phosphorus atom.
has W–Br (2) 2.618(2) and W–Br(3) 2.629(3). The
two W–C(diphenylacetylene) distances are equivalent
in both structures within experimental error.
1
The H-NMR spectra of complexes 1–8 (Table 2)
confirm the structure of 4 shown in Fig. 1. However,
all the spectra show a complex series of resonances
due to the likely existence of two diastereoisomers in
solution as has been observed previously for
[WI2(CO)(L-P,P%)(h2-MeC2R)] (R=Me or Ph) [21].
The 31P-NMR spectra (Table 2) of complexes 1–8
all show a high field resonance due to the uncoordi-
nated phosphine of the triphos ligand, PhP-
(CH2CH2PPh2)2 at ca. −13.5 ppm. The complexes
also all show at least three other resonances due to
the probable existence of diastereoisomers in solution,
as observed previously for related complexes [21].

268
P.K. Baker et al. / Journal of Organometallic Chemistry 580 (1999) 265–272
molybdenum
centre
in
[MoI2(CO)(L-P,P%)(h2-
After 30 min the resonance at −35.6 has disappeared
completely and the resonances for the finally isolated
MeC2Me)] in a slightly wet refluxing acetonitrile solu-
tion proceeds via initial oxidation of the
molybdenum(II) centre to the molybdenum(VI) species,
[MoI2(O)2(L-P,P%)], whereby the pendant phosphorus
atom is oxidised intramolecularly by one of the cis-
MoꢁO groups to give the finally isolated molybden-
um(IV) complex [MoI2(O){Ph2P(CH2)2PPh(CH2)2-
POPh2-P,P%,O}] (9), which has been characterised crys-
tallographically. This is only a postulate and further
studies are required in order to elucidate the mechanism
of this unusual reaction. Single crystals for X-ray crys-
tallography of 9 were grown by cooling (−17°C) a
concentrated CH2Cl2/Et2O solution (95:5) of 9 for 24 h.
The molecular structure of 9 is shown in Fig. 3, to-
gether with the atom numbering scheme. The atomic
coordinates and bond lengths and angles are given in
Table 3.
In the structure of 9, shown in Fig. 3, the oxidised
ligand is tridentate. As in [WI2(CO)(L-P,P%)(h2-
PhC2Ph)], two phosphorus atoms P(1) and P(4) are
chelating to the metal, but in addition O(8), which is
bonded to the third phosphorus atom P(7), is also
bonded to the metal making up a fac arrangement of
the tridentate ligand. The two phosphorus atoms are
both trans to iodine and the two Mo(1)–P distances are
bidentately
attached
linear
triphos
complex
[WI2(CO)(L-P,P%)(h2-PhC2Ph)] (see Fig. 2) are ob-
served. The resonance at −13 ppm is still observed
[21], and is due to the uncoordinated end phosphorus
atom in this complex. Similar results are obtained when
equimolar quantities of the bis(2-butyne) complex
[WI2(CO)(NCMe)(h2-MeC2Me)2] and L in CDCl3 at
10°C, again after 10 min a resonance at l= −33.6
ppm (triplet, JP–P=30 Hz) due to the uncoordinated
central phosphorus atom was observed.
The 13C-NMR spectrum (CD2Cl2, +25°C) for the
crystallographically characterised complex 4 shows,
apart from all the expected resonances (see Section 3),
an alkyne contact carbon resonance at l=219.7 ppm,
which suggests [25] the diphenylacetylene is donating
four electrons to the tungsten, which also enables it to
obey the effective atomic number rule.
Refluxing a slightly wet acetonitrile solution of
[MoI2(CO)(L-P,P%)(h2-MeC2Me)] (1) for 24 h gives the
oxidised molybdenum(IV) complex [MoI2(O){Ph2-
P(CH2)2PPh(CH2)2POPh2-P,P%,O}] · 0.5CH2Cl2 (9) in
80% yield. Complex 9 has been characterised by ele-
mental analysis (C, H and N) (Table 1) and by X-ray
crystallography. The complex was much less soluble in
CDCl3, CD2Cl2 and (CD3)2CO, hence it was very
˚
equivalent at 2.500(3), 2.505(3) A, while the coordina-
tion sphere is completed by a terminal oxygen atom
O(9) at 1.682(6) A from the metal which is trans to the
ligand O(8) (Mo(1)–O(8) 2.225(5) A).
1
difficult to obtain satisfactory H- and 31P-NMR spec-
˚
˚
tra for complex 9. It may be that the oxidation of the
Fig. 1. X-ray crystal structure of [WBr2(CO)(L-P,P%)(h2-PhC2Ph)] (4), together with the atomic numbering scheme. Ellipsoids shown at 30%
probability.

P.K. Baker et al. / Journal of Organometallic Chemistry 580 (1999) 265–272
269
Fig. 2. X-ray crystal structure of [WI2(CO)(L-P,P%)(h2-PhC2Ph)] (10), together with the atomic numbering scheme. Ellipsoids shown at 30%
probability.
This ligand has been found once only before in a
transition metal complex, also with molybdenum again
with a terminal oxygen in a trans position to the oxygen
of the ligand, viz bis(2,4,6-trimethylphenylseleno)ato-
oxo-fac-(2(diphenylphosphino)ethyl)phenylphosphino)-
ethyl)diphenylphosphineoxide molybdenum [26].
In conclusion, we have extended the series of
[MXY(CO)(L-P,P%)(h2-RC2R)] type complexes, and
found the structures of [WX2(CO)(L-P,P%)(h2-PhC2Ph)]
(X=Br, I) crystallise as single diastereoisomers, with
the same basic coordination geometry to the structures,
[WI2(CO)(L-P,P%)(h2-MeC2R)] (R=Me or Ph). The
interesting oxidation of both end phosphorus and the
molybdenum in [MoI2(CO)(L-P,P%)(h2-MeC2Me)] in
refluxing acetonitrile to give the crystallographically
characterised molybdenum(IV) complex [MoI2(O){Ph2-
P(CH2)2PPh(CH2)2POPh2-P,P%,O}]. We are currently
exploring the catalytic activity of complexes 1–9 as
alkene metathesis catalysts.
X=Y=I, R=Me [22] or Ph [23]; M=Mo, X=Y=
Br, R=Me or Ph [22]; M=W, X=Y=Br, R=Me or
Ph [11]; M=Mo or W, X=Cl (M=Mo only) or Br,
Y=I, R=Me or Ph [24]) were prepared by published
methods. The solvents used were all dried and purged
with dry nitrogen before use. All the chemicals used
were purchased from commercial sources and were used
without further purification.
Elemental analyses (C, H and N) were recorded on a
Carlo Erba Elemental Analyser MOD 1108 (using he-
lium as the carrier gas). Infrared spectra were recorded
as CHCl3 films between NaCl plates on a Perkin–Elmer
1
1600 series FTIR spectrophotometer. H-, 13C- (refer-
enced to SiMe4) and 31P-NMR (85% H3PO4) spectra
were recorded on a Bruker AC 250 NMR spectrometer.
3.1. Preparation of [WBr2(CO)(L-P,P%)(p2-PhC2Ph)]
(4)
To a solution of [WBr2(CO)(NCMe)(h2-PhC2Ph)2]
(0.2 g, 0.26 mmol) in CH2Cl2 (20 cm3) L (0.14 g, 0.26
mmol) was added, and the solution stirred for 17 h. The
resulting blue solution was filtered through celite and
the solvent removed in vacuo to yield a blue crystalline
powder of [WBr2(CO)(L-P,P%)(h2-PhC2Ph)] (4). It was
recrystallised from a solution of CH2Cl2/diethyl ether
80:20 cooled to −17°C, which afforded crystals suit-
able for X-ray crystallography. Yield=0.26 g, 91%.
The 13C-NMR (CDCl3, 25°C) has resonances at l=
3. Experimental
All reactions and purifications described in this paper
were carried out under an atmosphere of dry nitrogen
using standard vacuum/Schlenk line techniques. The
bis(alkyne) starting materials used in this research,
namely [MXY(CO)(NCMe)(h2-RC2R)2] (M=Mo,

270
P.K. Baker et al. / Journal of Organometallic Chemistry 580 (1999) 265–272
PhP(CH2CH2PPh2)2} in CH2Cl2 at room temperature
gave the bidentately attached triphos complexes
[MXY(CO)(L-P,P%)(h2-RC2R)] (M=Mo, X=Y=I,
R=Me or Ph; M=W, X=Y=Br, R=Me; M=W,
X=Br, Cl, Y=I, R=Me, Ph) (1–3, 5–8). For physi-
cal and analytical data see Table 1.
219.7 (s, CꢀC), 213.2 (s, CꢀO), 141.3–123.1 (m, Ph),
30.7 (m, PhPCH2), 25.0 (m, PhPCH2), 22.8 (m,
Ph2PCH2 and MeC2), 21.7 (m, Ph2PCH2) ppm.
Similar reactions of equimolar quantities of
[MXY(CO)(NCMe)(h2-RC2R)2]
and
L
{L=
Table 3
Selected molecular dimensionsa
3.2. Preparation of [MoI2(O){Ph2P(CH2)2-
PPh(CH2)2POPh2-P,P%,O}] · 0.5CH2Cl2 (9)
(a) Dimensions in the metal coordination sphere for 4 and 10
4 X=Br 10 X=I
A suspension of [MoI2(CO)(L-P,P%)(h2-MeC2Me)]
(0.5 g, 0.54 mmol) in NCMe (40 cm3) was refluxed for
24 h. The resultant dark brown solution was filtered
through celite and the solvent removed in vacuo to
W(1)–C(100)
W(1)–C(61)
W(1)–C(71)
W(1)–P(4)
W(1)–P(1)
W(1)–X(2)
W(1)–X(3)
1.981 (18)
2.024 (10)
2.019 (13)
2.005 (15)
2.489 (4)
2.589 (4)
2.618 (2)
2.629 (3)
2.018 (10)
2.040 (7)
2.513 (3)
2.563 (3)
2.816 (2)
2.840 (2)
afford
the
dark
brown
crystalline
powder
[MoI2(O){Ph2P(CH2)2PPh(CH2)2POPh2-P,P%,O}] · 0.5-
CH2Cl2 (9), yield=0.44 g, 80%. Crystals suitable for
X-ray crystallography of 9 were grown from a cooled
solution (−17°C) of CH2Cl2/diethyl ether (95:5).
C(100)–W(1)–C(61)
C(100)–W(1)–C(71)
C(61)–W(1)–C(71)
C(100)–W(1)–P(4)
C(61)–W(1)–P(4)
C(71)–W(1)-P(4)
C(100)–W(1)-P(1)
C(61)–W(1)-P(1)
C(71)–W(1)–P(1)
P(4)–W(1)–P(1)
C(100)–W(1)–I(2)
C(61)–W(1)–I(2)
C(71)–W(1)–I(2)
P(4)–W(1)–I(2)
113.1 (6)
110.0 (4)
71.9 (4)
38.1 (3)
94.4 (3)
92.8 (3)
93.4 (2)
162.9 (3)
86.7 (3)
124.5 (2)
80.92 (9)
91.0 (3)
75.6 (6)
38.1 (5)
89.9 (4)
90.3 (4)
96.9 (4)
3.3. X-ray crystallography
Crystals of 4, 9 and [WI2(CO)(L-P,P%)(h2-PhC2Ph)]
(10) suitable for X-ray crystallography were prepared as
described above. Crystal data are given in Table 4,
together with refinement details. Data for the com-
pounds were collected with Mo–Ka radiation using the
MARresearch Image Plate System. The crystals were
positioned at 75 mm [WI2(CO)(L-P,P%)(h2-PhC2Ph)]
(10) and 70 mm (4, 9) from the Image Plate. 95 frames
were measured at 2° intervals with a counting time of 2
min. Data analyses were carried out with the XDS
program [27]. The structures were solved using direct
methods with the SHELX86 program [28]. The non-hy-
drogen atoms were refined with anisotropic thermal
parameters. The hydrogen atoms were included in geo-
metric positions and given thermal parameters equiva-
lent to 1.2 times those of the atom to which they were
attached. All three structures were corrected for absorp-
tion using empirical methods [29]. The structures were
then refined on F2 using SHELXL [30]. The complexes
[WI2(CO)(L-P,P%)(h2-PhC2Ph)] (10 and 4) contained no
160.1 (4)
84.4 (5)
122.5 (4)
80.28 (13)
95.2 (4)
99.7 (4)
97.1 (4)
96.9 (3)
99.91 (19)
166.58 (6)
90.34 (8)
80.1 (3)
168.3 (3)
150.8 (2)
80.33 (7)
82.92 (8)
88.54 (4)
165.90 (10)
90.72 (12)
78.9 (4)
164.8 (3)
154.4 (4)
80.09 (11)
82.36 (9)
88.00 (9)
P(1)–W(1)–I(2)
C(100)–W(1)–I(3)
C(61)–W(1)–I(3)
C(71)–W(1)–I(3)
P(4)–W(1)–I(3)
P(1)–W(1)–I(3)
I(2)–W(1)–I(3)
(b) Dimensions in the metal coordination sphere for 9
Mo(1)–O(9)
Mo(1)–O(8)
Mo(1)–P(4)
Mo(1)–P(1)
Mo(1)–I(11)
Mo(1)–I(12)
1.682 (6)
2.225 (5)
2.500 (3)
2.505 (3)
2.827 (2)
2.859 (3)
O(9)–Mo(1)–O(8)
O(9)–Mo(1)–P(4)
O(8)–Mo(1)–P(4)
O(9)–Mo(1)–P(1)
O(8)–Mo(1)–P(1)
P(4)–Mo(1)–P(1)
O(9)–Mo(1)–I(11)
O(8)–Mo(1)–I(11)
P(4)–Mo(1)–I(11)
P(1)–Mo(1)–I(11)
O(9)–Mo(1)–I(12)
O(8)–Mo(1)–I(12)
P(4)–Mo(1)–I(12)
P(1)–Mo(1)–I(12)
I(11)–Mo(1)–I(12)
166.6 (2)
90.1 (2)
79.44 (16)
91.1 (2)
solvent, whereas
9 contained a dichloromethane
molecule which was refined with 50% occupancy. All
calculations were carried out on a Silicon Graphics
R4000 Workstation at the University of Reading.
79.13 (15)
81.30 (9)
100.2 (2)
89.67 (15)
168.73 (5)
93.89 (7)
98.8 (2)
90.49 (15)
95.25 (7)
169.49 (5)
87.68 (5)
Acknowledgements
M.M.M. thanks the EPSRC for a studentship. J.S.
thanks the Training for Work scheme for support. We
thank also A.W. Johans for help with the crystal struc-
ture determinations and the EPSRC and the University
of Reading for support for the Image Plate System.
a
˚
Distances given in A; angles given in degrees.

P.K. Baker et al. / Journal of Organometallic Chemistry 580 (1999) 265–272
271
Fig. 3. X-ray crystal structure of [MoI2(O){Ph2P(CH2)2PPh(CH2)2POPh2-P,P%,O}] (9), together with the atomic numbering scheme. Ellipsoids
shown at 30% probability.
Table 4
Crystal data and structure refinement details for the structures
Compound
4
10
9
Empirical formula
Formula weight
Crystal system
C49H43Br2OP3W
1084.41
Monoclinic
P21/a
C49H43I2OP3W
1178.39
Monoclinic
P21/a
C34.5H34ClI2MoO2P3
958.72
Monoclinic
P21/n
Space group
Unit cell dimensions
˚
a (A)
11.526(14)
16.577(17)
23.82(3)
(90)
92.57(1)
(90)
4546(9)
4, 1.584
4.439
14.927(14)
17.488(14)
17.819(14)
(90)
98.97(1)
(90)
4595(7)
4, 1.704
3.997
2280
12.341(13)
13.798(14)
22.97(2)
(90)
104.20(1)
(90)
3792(7)
4, 1.679
2.200
1868
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
Volume (A )
Z, calculated density (Mg m−3
)
Absorption coefficient (mm−1
F(000)
)
2136
Crystal size (mm)
q range for data collection (°)
Index ranges
0.35×0.25×0.15
2.70–25.99
−125h50
−205k520
−2851529
0.30×0.25×0.20
2.82–24.97
05h515
−205k520,
−2151520
0.25×0.20×0.20
2.58–25.98
05h515
−165k516
−2851527
Reflections
Collected/unique[Rint
]
12575/7325/(0.0603)
7325/0/505
0.0769
13634/7184[0.0326}
7184/0/505
0.0400
12284/7215 [0.0372]
7215/0/406
0.0605
Data/restraints/parameters
Final R indices [I\2|(I)] R1
wR2
0.2080
0.0990
0.1762
R indices (all data) R1
wR2
0.1306
0.2428
3.130, −2.403
0.0855
0.1582
1.147, −0.774
0.0853
0.2010
1.772, −1.001
Largest differential peak and hole (e A−3
)
.

272
P.K. Baker et al. / Journal of Organometallic Chemistry 580 (1999) 265–272
[14] T.G. Schenck, J.M. Downes, C.R.C. Milne, P.B. Mackenzie, H.
References
Boucher, J. Whelan, B. Bosnich, Inorg. Chem. 24 (1985) 2334.
[15] A. Blagg, P.G. Pringle, B.L. Shaw, J. Chem. Soc. Dalton Trans.
(1987) 1495.
[1] J.L. Templeton, Adv. Organomet. Chem. 29 (1989) 1 and refer-
ences cited therein.
[16] G.B. Jacobsen, B.L. Shaw, M. Thornton-Pett, J. Chem. Soc.
Dalton Trans. (1987) 1509.
[2] P.K. Baker, Adv. Organomet. Chem. 40 (1996) 45 and references
cited therein.
[17] S. Onaka, A. Mizuno, S. Takagi, Chem. Lett. (1989) 2037.
[18] T.S.A. Hor, L.-T. Phang, J. Organomet. Chem. 381 (1990) 121.
[19] T.S.A. Hor, L.-T. Phang, J. Organomet. Chem. 393 (1990) 345.
[20] M. Olmstead, C.H. Lindsay, L.S. Benner, A.L. Balch, J.
Organomet. Chem. 179 (1979) 289.
[3] J.L. Davidson, G. Vasapollo, J. Chem. Soc. Dalton Trans.
(1985) 2239.
[4] M.A. Bennett, I.W. Boyd, J. Organomet. Chem. 290 (1985) 165.
[5] P.B. Winston, S.J.N. Burgmayer, T.L. Tonker, J.L. Templeton,
Organometallics 5 (1986) 1707.
[21] P.K. Baker, S.J. Coles, D.E. Hibbs, M.M. Meehan, M.B. Hurst-
house, J. Chem. Soc. Dalton Trans. (1996) 3995.
[22] N. Aimeloglou, P.K. Baker, M.G.B. Drew, M.M. Meehan,
Polyhedron 17 (1998) 3455.
[6] E.M. Armstrong, P.K. Baker, M.E. Harman, M.B. Hursthouse,
J. Chem. Soc. Dalton Trans. (1989) 295.
[7] B.J. Brisdon, A.G.W. Hodson, M.F. Mahon, K.C. Molloy, R.A.
Walton, Inorg. Chem. 29 (1990) 2701.
[23] E.M. Armstrong, P.K. Baker, M.G.B. Drew, Organometallics 7
(1988) 319.
[24] P.K. Baker, M.G.B. Drew, M.M. Meehan, H.K. Patel, A.
White, J. Chem. Res. 379 (S) (1998) (M) 1461.
[8] A. Mayr, C.M. Bastos, J. Am. Chem. Soc. 112 (1990) 7797.
[9] A. Mayr, C.M. Bastos, R.T. Chang, J.X. Haberman, K.S.
Robinson, D.A. Belle-Oudry, Angew. Chem. Int. Ed. Engl. 31
(1992) 747.
[25] J.L. Templeton, B.L. Ward, J. Am. Chem. Soc. 102 (1980) 3288.
[26] P.M. Boorman, H.-B. Kraatz, M. Parvez, Polyhedron 12 (1993)
601.
[10] G.R. Clark, A.J. Nielson, A.D. Rae, C.E.F. Rickard, J. Chem.
Soc. Dalton Trans. (1994) 1783.
[11] P.K. Baker, D.J. Muldoon, A.J. Lavery, A. Shawcross, Polyhe-
dron 13 (1994) 2915.
[27] W. Kabsch, J. Appl. Cryst. 21 (1988) 916.
[28] SHELX86, G.M. Sheldrick, Acta Cryst., A46 (1990) 467.
[29] N. Walker, D. Stuart, Acta Cryst. A39 (1983) 158.
[30] SHELX1, G.M. Sheldrick, 1993, programme for crystal struc-
ture refinement, University of Go¨ttingen.
[12] A. Blagg, B.L. Shaw, M. Thornton-Pett, J. Chem. Soc. Dalton
Trans. (1987) 769.
[13] G.B. Jacobsen, B.L. Shaw, M. Thornton-Pett, J. Chem. Soc.
Dalton Trans. (1987) 1489.