Oxide bridged mixed metal organometallics: The reaction of Ru4(CO)13[μ3-PN(R)2] R = iPr, Cy with Cp*W(O)2CCPh

Article abstract of DOI:10.1016/S0022-328X(98)01037-7

The reaction of the tungsten oxo acetylide complex Cp*W(O)₂CCPh with Ru₄(CO)_12-13[μ₃-PN(R)₂] where R = ⁱPr or Cy affords two oxo bridged metal clusters η⁵-Cp*W(μ-O)Ru₄(CO) ₉(μ-CO)[μ₃-η²-P(O)N(R) ₂](μ₄-η²-CCPh) (2) and η⁵-Cp*W(μ-O)₂Ru₄(CO) ₁₀[μ₃-PN(R)₂](μ₄-η ²-CCPh) (3). X-ray analysis shows that 2 has a single W-O-Ru oxide bridge and contains the first example of a diisopropylaminophosphinidoxo ligand while in 3 both oxide ligands bridge W-Ru bonds. The reaction of 3 with HBF₄ · Et₂O forms the new W-F complex η⁵-Cp*WF(μ₃-O)HRu₄(CO) ₉[μ₃-η²-P(O)N(R)₂](μ ₄-η²-CCPh) (4).

Full text of DOI:10.1016/S0022-328X(98)01037-7

Journal of Organometallic Chemistry 577 (1999) 126–133
Oxide bridged mixed metal organometallics: the reaction of
i
Ru (CO) [m -PN(R) ] R= Pr, Cy with Cp*W(O) CCPh
4
13
3
2
2
a
b
a,b,
John H. Yamamoto , Gary D. Enright , Arthur J. Carty
*
a
Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Dri6e, Ottawa, Ontario K1A OR6, Canada
b
Department of Chemistry, Ottawa–Carleton Chemistry Institute, Uni6ersity of Ottawa, Ottawa, Ontario K1N 6N5, Canada
Received 16 October 1998
Abstract
The reaction of the tungsten oxo acetylide complex Cp*W(O) CCPh with Ru (CO)
i
[m -PN(R) ] where R= Pr or Cy affords
4
2
4
12–13
3
2
5
2
2
5
two oxo bridged metal clusters h -Cp*W(m-O)Ru (CO) (m-CO)[m -h -P(O)N(R) ](m -h -CCPh) (2) and h -Cp*W(m-
4
9
3
2
2
O) Ru (CO) [m -PN(R) ](m -h -CCPh) (3). X-ray analysis shows that 2 has a single W–O–Ru oxide bridge and contains the first
example of a diisopropylaminophosphinidoxo ligand while in 3 both oxide ligands bridge W–Ru bonds. The reaction of 3 with
HBF · Et O forms the new W–F complex h -Cp*WF(m -O)HRu (CO) [m -h -P(O)N(R) ](m -h -CCPh) (4). © 1999 Elsevier
2
4
10
3
2
4
5
2
2
4
2
3
4
9
3
2
4
Science S.A. All rights reserved.
Keywords: Phosphinidene; Phosphinidoxo; Tungsten; Ruthenium; Fluoride
1. Introduction
CCPh [5] has the appropriate functionality to coordi-
nate to transition metal carbonyl complexes. On the
The oxide (=O) group is normally considered to be
other
hand
the
nido-phosphinidene
clusters
a hard ligand in organometallic chemistry, principally
associated with early, high oxidation state metal frag-
ments [1]. However, recent developments suggest that
oxides can play an important role as interfacial ligands,
bridging early-high and late-low oxidation state metals
Ru (CO) (m -PR) are known to interact strongly with
4
13
3
alkynes, forming a variety of stable complexes in which
the acetylene coordinates on a square Ru P or Ru face
3
4
as a four-electron donor [6]. These two types of
molecules thus appear ideal to test the synthetic strat-
[
2] to form mixed metal oxo clusters which may serve as
models for oxide supported platinum metal catalysts
3]. In this paper we report the synthesis of several new
egy outlined above. The reaction of Cp*W(O) CCPh
2
with Ru (CO) [m -PN(R) ] (1) in refluxing hexane pro-
4
13
3
2
[
duced two types of oxide containing organometallic
5
oxide bridged early-late organometallic clusters. The
strategy we have employed is to deliver an early metal
oxo organometallic fragment to a late metal by using
the well known affinity of late metals for unsaturated
hydrocarbyls [4]. Although the number of early metal
oxo compounds bearing unsaturated hydrocarbyl lig-
clusters, one of which, h -Cp*W(m-O)Ru (CO) (m-
4
9
2
2
CO)[m -h -P(O)N(R) ](m -h -CCPh) (2) has W–O–Ru
and W–O–P interactions and contains the rare phos-
3
2
4
5
phinidoxo ligand RPO [3]. The other h -Cp*W(m-
2
O) Ru (CO) [m -PN(R) ](m -h -CCPh) (3) possesses
2
4
10
3
2
4
two oxide ligands bridging Ru–W bonds. Subsequent
ands is not very extensive, the molecule Cp*W(O)2-
reaction of 2 with HBF · Et O formed the new com-
4
2
5
2
plex h -Cp*WF(m -O)HRu (CO) [m -h -P(O)N(R) ](m -
h -CCPh) (4) with a W–F bond.
3
4
9
3
2
4
2
*
Corresponding author.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(98)01037-7

J.H. Yamamoto et al. / Journal of Organometallic Chemistry 577 (1999) 126–133
127
2
. Results and discussion
Ru1 the formation of a hinge of the butterfly cluster
between Ru2 and Ru4 and the oxidative addition of O1
to P to form the PO bond. The above rearrangement is
accomplished by a rotation of the acetylide ligand on
A potentially powerful methodology for constructing
oxide bridged mixed metal clusters consists of deliver-
ing an early metal oxo compound bearing an unsatu-
rated hydrocarbyl group to a late metal with an affinity
for hydrocarbyl p-electrons [4]. Using this strategy,
reaction of h -Cp*W(O) CCPh (Cp*=C Me ) [4] in
refluxing hexane for 3 h with the nido 62e- phos-
the WRu framework of 3 such that the tungsten atom
4
which is bonded to the tail [C(2)Ph] of the acetylide in
1
3 is attached in a h -fashion to the head [C(1)] in 2. It
5
is perhaps surprising, that in intermediate 3, the head of
2
5
5
the acetylide is not attached to tungsten, as in the
i
phinidene cluster Ru (CO) [m -PN( Pr) ] known to
strongly coordinate acetylenes, afforded two new com-
precursor
molecule
Cp*W(O) CCPh.
2
However,
4
13
3
2
acetylide bond isomerisation and structural rearrange-
ments have been observed previously in mixed metal
systems [7] and such transformations are more likely
than the alternative of phenyl group transfer between
acetylide carbon atoms.
5
2
plexes
h -Cp*W(m-O)Ru (CO) (m-CO)[m -h -P(O)N-
4
2 5
9
3
i
(
(
Pr) ](m -h -CCPh) (2a) and h -Cp*W(m-O) Ru -
2
4
2
4
i 2
CO) [m -PN( Pr) ](m -h -CCPh) (3) in 57 and 32%
1
0
3
2
4
yield, respectively. Similar compounds were formed but
As we have demonstrated elsewhere, the treatment of
transition metal clusters containing the diisopropy-
in quite different proportions when Ru (CO) [m -
4
13
3
PN(Cy) ] was used, with yields of 18.8 and 51.3% for
2
laminophosphinidene group with HBF · OEt followed
compounds 2b and 3b, respectively.
4
2
by hydrolysis causes oxidation of the phosphorus atom
to a PO ligand [8,9]. With this in mind compound 2 was
In refluxing heptane (30 min), 3a,b are converted
solely to 2a,b whereas 2 remains unchanged (Scheme 1).
Thus, 3 with two W–O–Ru bridges (vide infra) ap-
pears to be an intermediate in the reaction of
Cp*W(O) C Ph with 1. Cluster 2 on the other hand, in
treated with an excess of HBF · OEt . However, the
4
2
anticipated reaction did not occur and a new com-
5
2
pound 4, h -Cp*WF(m -O)HRu (CO) [m -h -P(O)N-
3
4
9
3
2
2
i
2
(
Pr) ](m -h -CCPh) with a W–F bond was isolated in
8% yield. The presence of tungsten fluorine bonds in 4
was verified via F-NMR spectroscopy. The F spec-
which oxidation of a phosphinidene ligand by a tung-
sten oxo functionality has occurred, is the thermody-
namic product of this reaction. The rearrangement of 2
to 3 can be described in terms of the cleavage of two
P–Ru bonds, the formation of bonds between P and
2
4
3
19
19
trum of 4a contained a doublet at −59.44 ppm with
3
JP–F of 15.26 Hz for 4a and for 4b a doublet at
3
−
59.23 ppm with J
of 13.73 Hz. Though it is not
P–F
unusual for an organometallic tungsten center in a high
oxidation state to react with a fluorinating reagent [10],
complex 4a is the first organometallic mixed metal
cluster to contain a fluoride ligand [10].
HBF · Et O has been previously used as a fluorinat-
4
2
ing agent for tungsten metal centers. For example the
treatment of WH (PPhMe ) with HBF · Et O in the
6
2 2
4
2
presence of CO leads to the cationic cluster [W (m-
2
F) (CO) (PPhMe ) ][BF ] [11]. The formation of a
3
4
2 4
4
metal–fluoride bond via reaction between a metal car-
bonyl and a fluorinating agent has been the subject of
two recent review articles [10].
The molecular structure of 2a (Fig. 1) consists of an
almost planar Ru butterfly (dihedral angle of 177.43°)
4
with the Cp*WC Ph fragment coordinated as a 4e-
2
donor on the Ru(2)Ru(3)Ru(4) triangle as a m3-h2-ꢀꢀ-
acetylene and with the tungsten atom asymmetrically
bridging the Ru(1)–Ru(2) bond (Ru(1)–W=2.9248(3);
˚
Ru(2)–W=2.7823(3) A). The most interesting features
of the cluster are associated with the oxide ligands
derived from the Cp*W(O) moiety. One oxygen atom,
2
O(2) acts as a bridge between tungsten and the phos-
phorus atom of the phosphinidene of 1a forming a
2
i
m -h diisopropylaminophosphinidoxo[OꢀPN( Pr) ] lig-
3
2
and on the Ru(1)–Ru(2)–W face. The P–O(2) bond
length (1.570(1) A) is comparable to that (P–O=
1.53(1)) in Fe (CO) (m -RPO) (R= Pr or Bu) the only
˚
i
t
Scheme 1.
3
10
3

128
J.H. Yamamoto et al. / Journal of Organometallic Chemistry 577 (1999) 126–133
5
5
Fig. 1. An ORTEP diagram of h -Cp*W(m-O)Ru (CO) (m-CO)[m -
Fig. 2. An ORTEP diagram of h -Cp*W(m-O) Ru (CO)10(m3-
4
9
3
2
4
2
i
2
i 2
h -OPN( Pr) ](m -h -CCPh) 2a showing 30% probability thermal el-
lipsoids. Hydrogen atoms are omitted for clarity. Selected bond
PN( Pr) )(m -h -CCPh) 3a showing 30% probability thermal ellip-
soids. Hydrogen atoms are omitted for clarity. Selected bond lengths
not mentioned in the text (A): W–Ru(1)=2.6910(5), W–Ru(2)=
3.0467(5), Ru(1)–Ru(2)=2.8154(7), Ru(1)–Ru(4)=2.8661(6),
Ru(2)–Ru(3)=2.7786(6), Ru(3)–Ru(4)=2.8393(7) and angles (°)
O(1)–W–O(2)=111.0(2).
2
4
2
4
˚
˚
lengths not mentioned in the text (A): W–Ru(1)=2.9248(3), W–
Ru(2)=2.7823(1), Ru(1)–Ru(2)=2.8428(4), Ru(1)–Ru(4)=
.8306(4), Ru(2)–Ru(3)=2.8802(4), Ru(2)–Ru(4)=2.7587(4),
Ru(3)–Ru(4)=2.6882(4) and angles (°) O(1)–W–O(2)=96.5(1), N–
P–O(2)=106.1(1).
2
for the 60 electrons predicted by the effective atomic
number rule [2e]. To accommodate this, the bonding is
thought to be best described as intermediate between
the forms WꢀO“Os and W–O–Os where the latter
represents an ether-like link between the two metals
other known m-RPO complexes [12] and is only slightly
longer than the PO distances in typical phosphine oxide
˚
complexes (e.g. PꢀO=1.4382(2) A in Ph PO) [13]. To-
3
˚
gether with the long W–O(2) distance (2.07(2) A) in-
dicative of a W–O single bond this suggests a PꢀO“W
(
Table 3).
interaction. Cluster 2a also has a W–O(1)–Ru(1)
The structure of 4a (Fig. 3) consists of four ruthe-
nium atoms arranged in a butterfly configuration (dihe-
˚
bridge (W–O(1)=1.759(2); Ru(1)–O(1)=2.227(2) A)
but in this case the oxide is double bonded to the
tungsten and the bonding is best described as WꢀO“
Ru. In this model W is in a +4 oxidation state and one
of the original oxo ligands has transferred to and
oxidized the phosphinidene ligand. Overall 2 is electron
precise (76 e-, 7 M–M) (Table 2).
In the second cluster 3a (Fig. 2) the Cp*W(O) C Ph
2
2
fragment is attached to a non-planar arrangement of
four ruthenium atoms (4Ru–Ru) via a m -acetylene,
4
two W–Ru bonds and two W–O–Ru oxide bridges.
From the W–O and Ru–O bond lengths (W–O(1)=
1
.815(4); W–O(2)=1.783(4); Ru(1)–O(1)=2.147(4);
˚
Ru(2)–O(2)=2.191(4) A), the metal-oxide interaction
is best represented as WꢀO“Ru for both bridging
oxides. In this case the tungsten atom is formally in a
+
6 oxidation state. Complex 3 is the first example of
an early-late metal organometallic cluster with two
oxide bridges to ruthenium. Overall 3 is electron rich
(
80 e-, 6 M–M). The tetrahedral organometallic cluster
5
Fig. 3. An ORTEP diagram of h -Cp*WF(m-O)HRu (CO) (m-
4
9
2
i
2
CpWOs (CO) (m-O) (m-H) with two bridging oxides
CO)(m
3
-h -OPN( Pr)
2
)(m -h -CCPh) 4a showing 30% probability ther-
mal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond
lengths not mentioned in the text (A): W–Ru(1)=2.8740(4), W–
Ru(3)=2.8895(4), Ru(1)–Ru(3)=2.7857(5), Ru(1)–Ru(4)=
.7685(4), Ru(2)–Ru(3)=2.7686(4), Ru(3)–Ru(4)=2.2.9271(4),
W–F 1.973(2).
4
3
9
2
would be counted as a 62 electron system and therefore
also electron rich if both oxides donated four-electrons.
However, the authors have counted each of the bridg-
ing oxide ligands as three-electron donors to account
˚
2

J.H. Yamamoto et al. / Journal of Organometallic Chemistry 577 (1999) 126–133
129
dral
angle
for
Ru(2)–Ru(3)–Ru(1)–Ru(4)=
3. Experimental
−138.58°) with the tungsten atom of the Cp*W(O)2-
CCPh ligand bridging a hinge of the butterfly. The
distance between W and Ru(2) is 3.4269(5) A which is
3.1. General data
˚
much longer than the sum of the covalent radii of W
Unless specified otherwise, all reactions were carried
out under an atmosphere of nitrogen. All solvents were
(
1.3) and Ru (1.33) [14]. This indicates that the tungsten
appropriately dried prior to use. HBF · Et O was pur-
atom and Ru(2) are not within bonding distance. The
acetylide ligand caps a triangular face of the butterfly.
The atom O(1) triply bridges W, Ru(3) and Ru(2)[W–
4
2
chased from Aldrich and used without further purifica-
i
i
tion. Ru (CO) [m -PN( Pr) ] [3], Ru (CO) [m -PN( Pr) ]
4
13
3
2
4
12
3
2
[
8], Ru (CO) [m -PN(Cy) ] [16] and Cp*W(O) CCPh
O(1)=1.955(2), Ru(3)–O(1)=2.116(2), Ru(2)–O(1)=
4
13
3
2
2
˚
[5] were synthesized by known procedures. TLC separa-
tions were performed in air using silica gel plates (60 A
F254) (Merck, 0.25 nm). Elemental analysis was carried
out by Ann Webb of the Institute of Biological Sciences
2
.061 (2) A]. This type of m -oxide ligand bridging
3
mixed metals is not uncommon and has been observed
before in related systems [15]. In this environment the
W atom is best described as being in a formal oxidation
state of +4. The aminophosphinidoxo ligand triply
bridges Ru(1), Ru(2) and W. The phosphorus atom lies
19
of the National Research Council of Canada F- and
3
1
P-NMR spectra were obtained with a Bruker DBX-
00 at 474.50 or 202.54 MHz, respectfully. IR spectra
5
across the edge formed by Ru(1) and Ru(2) and O(2) is
1
were recorded on
spectrometer.
a
Bio-Rad FTS-40A FTIR
h
bound to the tungsten atom. The P–O(2) bond
˚
distance is 1.559 (2) A which is indicative of a phospho-
rus oxygen double bond. For comparison the PꢀO
i
3
.2. Reaction of Ru (CO) [v -PN( Pr) ] with
˚
4
13
3
2
bond distance of Ph PO is 1.4383(2) A [13]. Together
3
Cp*W(O) CCPh
˚
2
with the long W–O(2) distance (2.116(2) A) which is
indicative of a W–O single bond, this suggests a PꢀO“
W interaction. With this coordination mode the phos-
phinidoxo ligand is formally donating 4e-. The
phosphinidoxo ligand observed in 4a is very similar to
i
To 25 mg of Ru (CO) [m -PN( Pr) ] (1a) (0.028
4
13
3
2
mmol) in a Schlenk tube was placed 13 mg of
Cp*W(O) CCPh (0.029 mmol) and 25 ml of dry hex-
ane. The mixture was refluxed for 3 h by which time the
solution had turned to a dark red–brown color. The
solution was dried in vacuo, and three compounds were
separated by TLC in air with a 1:2 CH Cl +hexane
2
1
the phosphinidoxo ligand in 3a (vide-infra). An h -
fluoride ligand is attached to the tungsten atom adja-
cent to both O(2) and C(1). The hydride ligand bridging
Ru3 and Ru4 was located in an electron density map
and its position was refined isotropically. The existence
of a hydride ligand was also confirmed by the observa-
tion of a singlet resonance in the proton NMR spec-
trum at −20.54 ppm which is a typical chemical shift
for a bridging hydride. Overall 4 is electron precise (76
e-, 7 M–M) (Table 4).
2
2
mixture. The compounds were in order of elution:
i
Ru (CO) (1 mg, 5.7%), Ru (CO) [m -PN( Pr) ] (1 mg,
3
12
5
13
4
2 ,
2
5
.6%)
and
Cp*W(m-O)Ru (CO) (m-CO)[m -h -
4
9
3
i
2
OPN( Pr) ](m -h -CCPh) (18 mg, 57%); 2a. The base
2
4
line was then eluted with pure CH Cl and an orange
2
2
band was isolated. This band contained Cp*W(m-
i
2
O) Ru (CO) [m -PN( Pr) ](m -h -CCPh) (10 mg, 0.0089
2
4
9
3
2
4
Addition of fluoride ion to the tungsten center
initiates a rearrangement of the metal framework.
This rearrangement can be accounted for by the cleav-
age of the butterfly hinge bond (Ru4–Ru2), and the
W–Ru1 bond, as well as the transformation of the
bridging carbonyl to a terminal one. Concurrently, a
new hinge bond is formed between Ru1–Ru3 and
bonds are generated between W–Ru4 and O1–Ru4. A
bridging hydride is also incorporated between Ru3 and
Ru4.
In summary, new types of stable oxide bridged
mixed metal organometallic clusters can be accessed
via reaction of high oxidation state oxo acetylides
with late metal carbonyl complexes. We are currently
examining the potential of this methodology for
the introduction of oxide ligands into other mixed
oxidation state organometallic clusters and for the
generation of new oxidized phosphide supporting lig-
ands.
mmol, 32%); 3a. Spectral data for Cp*W(m-
2
i
2
O)Ru (CO) (m-CO)[m -h -OPN( Pr) ](m -h -CCPh) 2a:
4
9
3
2
4
IR, (w (CO) in hexane), 2065(s), 2027(s), 2015(vs),
−1
2
(
1
001(m), 1981(m), 1965(w), 1960(vw) cm . IR, (w
CO) in CH Cl ), 2060(s), 2022(vs), 2009(s), 1994(m),
2
2
−1
1
976(m), 1957(w), 1985(w) cm
.
H-NMR, (l in
CDCl ), 7.80 (1H, d, JH–H=7.9), 7.49 (1H, dd, JH–H
.7, JH–H=7.9), 7.20 (2H, dd, JH–H=7.9, JH–H=7.4),
.20 (1H, dd, JH–H=6.7, JH–H=7.9), 6.78 (1H, d,
JH–H=7.4), 3.88 (1H, q, JH–H=6.8), 3.75 (2H, q,
JH–H=6.8), 2.00 (s, 15H), 1.43 (6H, d, JH–H=6.8),
.37 (6H, d, JH–H=6.8). P-NMR, (l in CDCl3),
=
3
6
7
31
1
248(s). Anal. Calc. for 2a: C, 32.11, H, 2.70, N, 1.10.
Found: C, 31.40, H, 2.61, N, 1.36%. Spectral data for
i
2
Cp*W(m-O) Ru (CO) [m -PN( Pr) ](m -h -CCPh)
3a:
2
4
9
3
2
4
IR, (w (CO) in hexane), 2071(s), 2036(s), 2021(vs),
−
1
2006(s), 1986(m), 1966(w), 1949(m) cm . IR, (w (CO)
in CH Cl ), 2070(m), 2036(s), 2016(vs), 2002(m),
2
2
−
1
1
1994(m), 1958(w), 1939(w) cm
.
H-NMR, (l in

130
J.H. Yamamoto et al. / Journal of Organometallic Chemistry 577 (1999) 126–133
CDCl ), 8.55 (1H, d, JH–H=7.6), 7.59 (1H, dd, JH–H
=
(dd, 2H, JH–H=7.32, JH–H=7.38), 7.15 (dd, 1H, JH–
H=7.34, JH–H=6.90), 6.23 (d, 1H, JH–H=7.79) 3.56
(m, 2H), 1.85 (s, 15H), 1.82–1.32 (m, 20H). P-NMR,
3
6
3
.9, JH–H=7.4), 7.19 (2H, m), 6.19 (1H, d, JH–H=7.4),
31
.92 (2H, m), 1.83 (s, 15H), 1.30(d, 15H, JH–H=6.83).
3
1
P-NMR, (l in CDCl ), 356 (bs). Anal. Calc. for 3a: C,
(l in CDCl ), 364 (bs). Anal. Calc. for 3b: C, 34.30, H,
3
3
3
1
1.92, H, 2.60, N, 1.13. Found: C, 31.81, H, 2.35, N,
.21%.
3.27, N, 1.08. Found: C, 34.45, H, 3.54, N, 1.34%.
3.5. Thermolysis of 2a
i
3
.3. Reaction of Ru (CO) [v -PN( Pr) ] with
4
12
3
2
Cp*W(O) CCPh
2
To 25 mg of 2a (0.019 mmol) in a Schlenk tube was
placed 20 ml of dry heptane and the red–brown solu-
tion was refluxed for 3 h. The reaction was then dried
in vacuo and the crude solid was separated on a silica
TLC plate with a 1:2 CH Cl +hexane solvent system.
i
To 18 mg of Ru (CO) [m -PN( Pr) ] (0.021 mmol) in
4
12
3
2
a Schlenk tube was placed 9 mg of Cp*W(O) CCPh
0.020 mmol) and 25 ml of dry hexane. The solution
was refluxed for 3 h by which time the solution had
turned to a dark red–brown color. The solution was
dried in vacuo, and three compounds were separated by
TLC in air with a 1:2 CH Cl +hexane mixture as an
eluting solvent system. The compounds were in order of
elution: Ru (CO) (1 mg, 7.6%), Ru (CO) [m -
PN( Pr) ] (2 mg, 8.6%) and 2a (10 mg, 0.0089 mmol,
2%). The base line was then eluted with pure CH Cl2
an a orange band was isolated. This band was deter-
2
(
2
2
Two compounds were isolated: Ru (CO) (1 mg, 7.9%)
3
12
and compound 2a (8 mg, 0.063 mmol, 32%).
2
2
3.6. Thermolysis of 3a
3
12
5
13
4
In a Schlenk tube 23 mg of 3a (0.0186 mmol) was
i
2
,
mixed with 20 ml of dry heptane and the orange
solution was then refluxed for 30 min. The red–brown
reaction mixture was then dried in vacuo and the crude
material was then separated on a silica TLC plate with
a 1:2 CH Cl +hexane solvent system. Two compounds
4
2
mined to be 3a (8 mg, 0.0071 mmol, 34%).
2
2
3
.4. Reaction of Ru (CO) [v -PN(Cy) ] with
4 13 3 2
were separated: Ru (CO) (1 mg, 8.4%) and compound
3
12
Cp*W(O) CCPh
2
2
a (17 mg, 0.0139 mmol, 72%).
To 400 mg of Ru (CO) [m -PN(Cy) ] 1b (0.40 mmol)
4
13
3
2
3.7. Thermolysis of 2b
in
a
Schlenk tube was placed 184 mg of
Cp*W(O) CCPh (0.40 mmol) and 25 ml of dry hexane.
2
As described above for 2a, 182 mg of 2b (0.1375
The solution was refluxed for 3 h by which time the
solution was a dark red–brown color. The solution was
dried in vacuo. Three compounds were separated by
TLC in air with a 1:2 CH Cl +hexane mixture. The
mmol) and 20 ml of dry heptane were refluxed for 3 h.
The red–brown reaction mixture was then dried in
vacuo and the crude products were separated on a silica
TLC plate with a 1:2 CH Cl +hexane solvent system.
2
2
2
2
compounds were in order of elution: Ru (CO) (23 mg,
3
12
Two compounds were isolated: Ru (CO) (5 mg, 5.6%)
3
12
9
.0%), Ru (CO) [m -PN(Cy) ] (35 mg, 7.7%), and
5
15
4
2 ,
2 2
and compound 2b (130 mg, 0.0982 mmol, 71%).
Cp*W(m-O)Ru (CO) (m-CO)[m -h -P(O)N(Cy) ](m -h -
CCPh) (89 mg, 0.07 mmol, 18.8%) 2b. The base line
4
9
3
2
4
3
.8. Thermolysis of 3b
was then eluted with pure CH Cl and an orange band
2
2
was isolated. This band was determined to be Cp*W(m-
2
Refluxing an orange solution of 140 mg of 3b (0.1080
O) Ru (CO) [m -PN(Cy) ](m -h -CCPh) 3b (243 mg,
2
4
9
3
2
4
mmol) and 10 ml of dry heptane for 30 min gave a
red–brown solution. The reaction mixture was then
dried in vacuo and separation of the compounds on a
0
.20 mmol, 51.3%). Spectral data for Cp*W(m-
2 2
O)Ru (CO) (m-CO)[m -h -P(O)N(Cy) ](m -h -CCPh) 2b:
4
9
3
2
4
IR, (n (CO) in hexane), 2064(s), 2027(s), 2014(vs),
000(m), 1980(m), 1965(w), 1959(w), 1937(vw), 1890(w)
silica TLC plate with a 1:2 CH Cl +hexane solvent
2
2
2
−
1
1
system afforded two compounds: Ru (CO) (1 mg,
cm . H-NMR, (l in CDCl ), 7.81(d, 1H, JH–H=8.5),
3 12
3
1
.4%) and compound 2b (97 mg, 0.0733 mmol, 68%).
7.49(t, 1H, JH–H=8.2, JH–H=8.5), 7.22 (t, 1H, JH–
H=8.2, JH–H=7.4), 7.14 (t, 1H, JH–H=7.8, JH–H
=
7
1
2
.4), 6.78 (d, 1H, JH–H=7.8), 3.45 (m, 2H), 2.01 (s,
5H), 1.85–1.09 (m, 20H). P-NMR, (l in CDCl3),
47(s). Anal. Calc. for 2b: C, 34.48, H, 3.20, N, 1.06.
3.9. Reaction of 2a with HBF · Et O
4
2
3
1
A CH Cl solution of 2a (80 mg, 0.063 mmol) was
2
2
Found: C, 34.01, H, 2.85, N, 1.15%. Spectral data for
stirred under an atmosphere of nitrogen gas at 25°C for
2
Cp*W(m-O) Ru (CO) [m -PN(Cy) ](m -h -CCPh)
3b:
24 h with 100 ml of HBF · Et O. The solution was then
2
4
9
3
2
4
4
2
IR, (w (CO) in hexane), 2070(w), 2036(s), 2020(vs),
dried in-vacuo and the dark red residue was placed on
−
1
2004(m), 1995(m), 1985(w), 1965(vw), 1948(m) cm
.
to a silica gel plate. A 50:50 CH Cl +hexane solution
2
2
1
H-NMR, (l in CDCl ), 8.60 (d, 1H, JH–H=7.85), 7.24
was used as the eluting solvent and a single compound
3

J.H. Yamamoto et al. / Journal of Organometallic Chemistry 577 (1999) 126–133
131
Table 1
Crystallographic data for compounds 2a, 3a and 4a
Formula
WRu PO12NC34H34
WRu PO12NC34H34 · CH Cl
WRu PFO11NC33H35
4
4
2
2
4
Formula weight
Crystal system
1267.73
1352.69
Triclinic
11.2133(1)
12.0983(1)
16.9326(1)
73.04(1)
87.20(1)
74.75(1)
2118.87(3)
0.03×0.15×0.20
P1 (no. 2)
2
1258.72
Triclinic
11.5202(1)
11.4924(1)
16.3814(2)
91.91(1)
108.58(1)
108.35(1)
1926.52(6)
0.150×0.150×0.045
P1 (no. 2)
2
Monoclinic
13.0014(2)
21.4552(3)
14.7878(3)
90
107.96(1)
90
3924.1(1)
0.20×0.20×0.20
˚
a (A)
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
˚
3
V (A )
Crystal dimensions(mm)
Space group
P2 /n (no. 14)
1
Z value
4
2.14
4.53
zcalc. (Mg m−3)
2.12
4.35
2.17
4.61
v (Mo–K ) (mm−1)
a
T (°C)
−150
57.3
−150
57.5
−150
57.5
2
[max (°)
No. of reflections measured
No. of unique reflections
No. of reflections observed [I\2.5|(I)]
No. of variables
27168
10104
8270
17866
10556
8203
506
22519
9835
8400
469
615
Goodness-of-fit
0.92
1.26
1.43
Max shift in final cycle
Residuals: R; Rw
0.00
0.163
0.00
0.025; 0.028
Empirical
1.59
0.038; 0.043
Empirical
2.08
0.025;0.026
Empirical
1.20
Abs. Cor.
Largest peak in final difference map (e A−2)
˚
5
2
3
was
isolated
h -Cp*WF(m -O)HRu (CO) [m -h -
CF COOH), −59.23 (d, JP-F=13.73). Anal. Calc. for
3
4
9
3
3
i
2
P(O)N( Pr) ](m -h -CCPh) 4 (23 mg, 0.018 mmol, 28%).
Spectral data for 4a: IR, (w (CO) in CH Cl ), 2080(s),
038 (vs), 1999(s), 1982 (sh), 1953(m), 1929(w) cm
4b: C, 33.96, H, 3.23, N, 1.04. Found: C, 33.63, H, 3.58,
2
4
N, 0.96%.
2
2
−
1
2
.
1
H-NMR, (l in CDCl ), 7.83 (d, 2H, JH–H=7.38), 7.61
3
3.11. Crystallographic analyses
(
dd, 1H, JH–H=7.50, JH–H=7.38), 7.51 (dd, 2H, JH–
H=7.50, JH–H=7.38) 3.51 (m, 2H), 2.32 (s, 15H), 1.28
Orange crystals of 3a suitable of X-ray diffraction
analysis were grown by slow evaporation of a 1:2
CH Cl +hexane solution at −20°C. Red crystals of
2a and 4a suitable for X-ray diffraction analysis were
grown from benzene and hexane solutions, respectively,
at 20°C. The crystals used in the diffraction measure-
ments were mounted on a glass fiber with 5 min epoxy.
Diffraction measurements were made on a Siemens
SMART CCD automatic diffractometer by using
3
1
(
m, 6H) -20.4 (1H, s). P-NMR, (l in CDCl ), 315 (s).
3
1
9
F-NMR, (l in CDCl vs. CF COOH), −59.44 (d,
3
3
2
2
3
JP–F=15.26). Anal. Calc. for 4a: C, 31.71, H, 2.74, N,
1.09. Found: C, 31.43, H, 2.85, N, 1.23%.
3
.10. Reaction of 2b with HBF · Et O
4
2
A CH Cl solution of 2b (56 mg, 0.042 mmol) was
2
2
stirred under an atmosphere of nitrogen gas at RT for
graphite-monochromated Mo–K radiation. The unit
a
3
0 min with 100 ml of HBF · Et O. The solution was
cells were determined from randomly selected reflec-
tions obtained by using the SMART CCD automatic
search, center, index and least-square routines. Crystal
data, data collection parameters, and results of the
analyses are listed in Table 1. All data processing was
performed on a silicon graphics INDY computer by
using the NRCVAX [17] structure solving library ob-
tained from the National Research Council of Canada,
Ottawa, Ontario. Neutral atom scattering factors were
calculated by the standard procedures [18]. Anomalous
dispersion corrections were applied to all non-hydrogen
atoms [19]. Lorentz/polarization (Lp) and absorption
corrections were applied to the data for the structure
4
2
then dried in vacuo and the dark red residue was placed
on to a silica gel plate. A 50:50 CH Cl +hexane
solution was used as the eluting solvent affording a
2
2
5
2
single product. h -Cp*WF(m -O)HRu (CO) [m -h -
3
4
9
3
i
2
P(O)N( Pr) ](m -h -CCPh) 4b. (22 mg, 0.0164 mmol
2
4
3
2
9%). Spectral data for 4b: IR, (w (CO) in hexane),
080(s), 2018(vs), 2000(s), 1983(sh), 1953(m), 1929(w)
−
1
1
cm . H-NMR, (l in CDCl ), 7.77 (d, 2H, JH–H=
3
7.7), 7.33 (t, 2H, JH–H=7.3, JH–H=7.7), 7.25 (t, 2H,
JH–H=7.3, JH–H=7.9), 3.21 (m, 2H), 2.19 (s, 15H),
31
1.72-1.26 (m, 20H) −21.4 (1H, s). P-NMR, (l in
1
9
CDCl3), 188(s).
F-NMR, (l in CDCl3 versus

132
J.H. Yamamoto et al. / Journal of Organometallic Chemistry 577 (1999) 126–133
Table 2
Selective intramolecular bond lengths (A) and angles (°) for h -
Table 4
˚
5
˚
5
Selective intramolecular bond lengths (A) and angles (°) for h -
Cp*WF(m-O)HRu (CO) [m -h -P(O)N( Pr) ](m -h -CCPh) 4a
2
i
2
2
i
2
Cp*W(m-O)Ru (CO) (m-CO)(m -h -OPN( Pr) (m -h -CCPh) 2a
4
9
3
2
4
4
10
3
2
4
˚
˚
Bond lengths (A)
Bond lengths (A)
W–Ru(2)
W–C(1)
W–O(2)
Ru(2)–Ru(3)
Ru(2)–C(1)
Ru(1)–O(1)
Ru(4)–C(2)
P–O(2)
2.7823(3)
2.050(3)
2.0743(21)
2.8802(4)
2.149(3)
2.2270(24)
2.279(3)
1.570(3)
1.374(4)
W–Ru(1)
W–O(1)
2.9248(3)
1.7589(24)
2.8428(4)
2.7587(4)
2.8306(4)
2.6882(4)
2.244(3)
Ru(1)–Ru(3)
Ru(1)–W
Ru(2)–O(1)
Ru(3)–W
Ru(3)–C(1)
W–F
W–O(2)
P–N
C(1)–C(2)
2.7857(5)
2.8740(4)
2.0612(23)
2.8895(4)
2.167(3)
1.9731(19)
2.1166(22)
1.640(3)
Ru(1)–Ru(4)
Ru(2)–Ru(3)
Ru(3)–Ru(4)
Ru(3)–O(1)
Ru(4)–C(2)
W–O(1)
2.7685(4)
2.7686(4)
2.9271(4)
2.1164(22)
2.072(3)
1.9549(23)
1.966(3)
1.5586(25)
Ru(2)–Ru(1)
Ru(2)–Ru(4)
Ru(1)–Ru(4)
Ru(3)–Ru(4)
Ru(4)–C(1)
P–N
W–C(1)
P–O(2)
1.641(3)
C(2)–C(1)
1.401(5)
Bond angles (°)
O(1)–W–O(2)
W–P–O(2)
Bond angle (°)
O(1)–W–O(2)
96.53
48.09(8)
W–O(2)–P
O(2)–P–N
97.62(11)
106.10(14)
80.81(9)
Torsion angle (°)
Ru3–Ru2–Ru4–Ru1 177.43
4. Supplementary material
Texts describing the experimental details for com-
plexes 2a, 3a and 4a, full details of crystal structure
analyses including tables of bond distances and angles,
atomic coordinates, anisotropic thermal parameters (29
pages). This material is available from the authors on
request.
solution. Full matrix least-squares refinements mini-
2
mized the function: S w(ꢀF ꢀ−ꢀF ꢀ) where w=1/
hkl
o
c
2
2
2
|
(F )2, |(F )=|(F )/2F and |(F )=[|(I ) +
o o o o o raw
0.02Inet) ] /Lp.
The crystallographic space group P2 /n was uniquely
2
1/2
(
1
identified for compound 2a by the pattern of systematic
absences observed during the collection of intensity
data. For compounds 3a and 4a the space group P1
was assumed and confirmed by successful solution and
refinement of the structure. All structures were solved
by a combination of direct methods (SOLVER) and
difference Fourier syntheses. All non hydrogen atoms
were refined with anisotropic thermal parameters.
Acknowledgements
This work was supported by grants from the Na-
tional Research Council of Canada and the Natural
Sciences and Engineering Research Council of Canada
(
to A.J.C.). We are very grateful to Professor Y. Chi
for a sample of Cp*W(O) C Ph.
2
2
References
Table 3
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Selective intramolecular bond lengths (A) and angles (°) for h -
Cp*W(m-O) Ru (CO) (m -PN( Pr) (m -h -CCPh) 3a
i
2
2
4
10
3
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4
˚
Bond lengths (A)
W–Ru(1)
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Ru(4)–Ru(1)
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Ru(3)–C(1)
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