Reactions of 1,8-bis(diphenylphosphino)naphthalene with ruthenium cluster carbonyls: C-H and C-P bond cleavage reactions

Article abstract of DOI:10.1016/j.ica.2004.01.022

Reactions between Ru₃(CO)₁₂ and 1,8- bis(diphenylphosphino)naphthalene (dppn) have given the four complexes Ru ₃(μ-H){μ₃-PPh₂(nap)PPh(C ₆H₄)}(CO)₈ (1), Ru₄(

Full text of DOI:10.1016/j.ica.2004.01.022

Inorganica Chimica Acta 357 (2004) 1805–1812
www.elsevier.com/locate/ica
Reactions of 1,8-bis(diphenylphosphino)naphthalene with
ruthenium cluster carbonyls: C–H and C–P bond cleavage reactions
a,
a
b
b
Michael I. Bruce *, Paul A. Humphrey , Sakir Okucu , Reinhard Schmutzler ,
c
Brian W. Skelton , Allan H. White
c
a
Department of Chemistry, University of Adelaide, Adelaide, South Australia 5005, Australia
Institut fu€r Anorganische und Analytische Chemie, Technische Universita€t Braunschweig, 38106 Braunschweig, Germany
Department of Chemistry, University of Western Australia, Crawley, Western Australia 6009, Australia
b
c
Received 2 October 2003; accepted 16 December 2003
Dedicated to Professor Helmut Werner on the occasion of his 70th birthday, with respect and admiration
Abstract
Reactions between Ru3(CO)12 and 1,8-bis(diphenylphosphino)naphthalene (dppn) have given the four complexes Ru3(l-H){l3-
PPh2(nap)PPh(C6H4)}(CO)8 (1), Ru4(l-H){l3-PPh2(nap)PPh(C6H4)}(l-CO)3(CO)7 (2) and Ru4(l-H)(l3-C6H4){l-PPh(nap)PPh2}-
(CO)11 (3) (in refluxing thf), and Ru4{l4-P(nap)PPh2}(l4-C6H4)(l-CO)(CO)9 (4) (in refluxing toluene) which have been
characterised by single crystal X-ray studies. They have been formed by aryl C–H and aryl C–P bond cleavage reactions, presumably
from an initial (unobserved) chelate dppn complex. The unchanged chelating ligand is found in Ru3(l-dppm)(CO)8(dppn) (5),
obtained from Ru3(l-dppm)(CO)10 and dppn in refluxing thf.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Ruthenium cluster; Phosphine complexes; X-ray structure; Bond cleavage (C–H, C–P)
1. Introduction
ButPh) have also been made [7]. Our interest in the co-
ordination and subsequent bond-cleavage reactions of
bidentate phosphines on metal clusters suggested that
the close approach of the two phosphorus atoms might
induce some unusual reactivity in complexes with
polynuclear metal systems and we have instigated a
survey of the reactions of dppn with trinuclear Group 8
metal carbonyl clusters. This paper describes some
complexes obtained from reactions between dppn and
Ru3(CO)10(L)2 [L2 ¼ (CO)2, dppm].
The metal complex chemistry of 1,8-bis(diph-
enylphosphino)naphthalene (dppn), a phosphorus ana-
logue of 1,8-bis(dimethylamino)naphthalene (‘‘proton
spongeÒ’’), has attracted attention since the first report
of this highly basic phosphine [1]. The two phosphorus
ꢀ
atoms are 3.0483 (6) A apart, i.e. within the sum of the
ꢀ
van der Waals radii (3.80 A), and thus have a rigid
chelating interaction with metal centres. Conventional
chelate complexes MLn(dppn) (MLn ¼ Mo(CO)4 [2],
PdCl2, PtCl2 [1,2], [Pd(g-C3H5)]þ [3]) have been de-
scribed, while more recently, accounts of gold(I) and
gold(II) complexes [Au(dppn)2]Cl [4], {Au(CꢀCAr)}2
(l-dppn) [5] and [{AuX(dppn)}2]2þ (X ¼ Br, I), the
latter containing an unsupported Au(II)–Au(II) bond
[6], have appeared. Platinum(II) complexes of 1,8-
(PRR0)2naphthalenes (RR0 ¼ Me2, Me(C6F5), Cy2,
2. Results and discussion
The reaction between Ru3(CO)12 and dppn was car-
ried out in refluxing thf and unusually, did not require
any initiator for a rapid reaction to ensue. After re-
fluxing the mixture for 5.5 h, all starting cluster carbonyl
had been consumed and preparative t.l.c. on silica gel
separated three complexes in a total yield of 48%. Trace
amounts of other, presently unidentified, complexes
* Corresponding author. Fax: +61-8-8303-4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.01.022

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M.I. Bruce et al. / Inorganica Chimica Acta 357 (2004) 1805–1812
were observed. The pure complexes were identified by
single crystal X-ray structural determinations, spectro-
scopic data being consistent with the solid-state struc-
tures being preserved in solution.
Two of the complexes contain the cyclometallated
(dppn-H) ligand. Plots of their structures are shown
in Fig. 1, with selected bond parameters in Table 1.
The faster running of these (Rf 0.56) is Ru3(l-H)
{l3-PPh2(nap)PPh(C6H4)}(CO)8 (1; nap ¼ 1,8-C10H6)
which formed red crystals (from CH2Cl2/hexane). One
phenyl group of a molecule of dppn has oxidatively
added to the cluster to give a C6H4 group which bridges
1
2
ꢀ
the Ru(2)–Ru(3) bond [2.7078(5) A] in the g :g bond-
ing mode [Ru(3)–C(112) 2.120(4), Ru(2)–C(111, 112)
ꢀ
2.411, 2.323(4) A]. The H atom is found bridging Ru(1)–
ꢀ
Ru(3) [1.80, 1.76(5) A] which has lengthened to
ꢀ
2.9926(4) A as a consequence. As expected, the two P
atoms chelate Ru(1) in axial and equatorial positions
ꢀ
[Ru(1)–P(1,2) 2.296, 2.308(1) A]. The bite angle of P(1,2)
at Ru(1) is 84.43(3)°. The coordination about the metal
atoms is completed by eight CO groups, two on Ru(1)
and three each on Ru(2,3). The complex has a 48 cluster
valence electron (c.v.e.) count with three Ru–Ru bonds.
Bright orange crystals of tetranuclear Ru4(l-H)(l3-
C6H4){l-PPh(nap)PPh2}(CO)11 (3; Rf 0.50) contain an
unusual spiked triangular cluster, in which the Ru(1)–
Ru(2) fragment carries the two P atoms and associated
groups (see Fig. 2 and Table 2). The Ru(1)–Ru(2) vector
is inclined at an angle of 58.50(3)° to the plane of
the Ru3 triangle. The dppn ligand has fragmented into the
phosphido–phosphine PPh(nap)PPh2 which bridges the
ꢀ
Ru(1)–Ru(2) bond [2.8705(4) A], a C6H4 ring (benzyne)
which caps the triangular cluster in the g1:g1:g2 mode
[Ru(2)–C(02) 2.108(3), Ru(3)–C(01) 2.088(3), Ru(4)–
ꢀ
C(01,02) 2.297, 2.245(3) A], and an H atom bridging
ꢀ
Ru(2)–Ru(3) [3.0014(4); Ru(2,3)–H 1.73, 1.77(4) A].
Eleven CO groups are distributed three each to
Ru(1,3,4) and two on Ru(2). Atom Ru(1) is chelated by
the two phosphorus atoms [Ru–P(1,2) 2.3092, 2.3377(8)
ꢀ
A], but having lost a Ph group, atom P(2) is also at-
ꢀ
tached to Ru(2) [2.3287(8) A]. The chelate bite angle at
Ru(1) is 86.27(3)°. The c.v.e. count is 64, as expected for
an M4 cluster with four M–M bonds.
The second complex, Ru4(l-H){l3-PPh2(nap)PPh-
(C6H4)}(l-CO)3(CO)7 (2; Rf 0.42) forms dark brown–
black crystals. The structure (Fig. 1b; bond distances and
angles in Table 1) is based on a tetrahedral Ru4 core,
formed by fusion of an Ru(CO)2 unit to 1, below the Ru3
plane. The fourth Ru atom caps the other side of the Ru3
triangle, being attached via three Ru–Ru bonds [Ru(1,2,3)–
02
01
108
Ph
P2
Ru4
(CO)3
Ru2
Ru3(CO)3
101
(CO)2
ꢀ
Ru(4) 2.8836, 2.7128, 2.7493(7) A] and supported by one
Ph2P1
H
fully bridging and two semi-bridging CO ligands. One face
of the tetrahedron supports a PPh2(nap)PPh(C6H4) ligand
attached as found in 1 above. Thus, the C6H4 group
Ru1
(CO)3
1
2
(3)
ꢀ
bridges the Ru(2)–Ru(3) bond [2.8238(7) A] in the g :g
bonding mode [Ru(3)–C(112) 2.120(5), Ru(2)–C(111, 112)
ꢀ
2.314, 2.302(5) A]. The two P atoms chelate Ru(1) in axial
ꢀ
and equatorial positions [Ru(1)–P(1,2) 2.320, 2.341(1) A]
The only complex which was characterised from a
similar reaction carried out under more vigorous con-
ditions (refluxing toluene) was Ru4{l4-P(nap)PPh2}(l4-
C6H4)(l-CO)(CO)9 (4), which formed orange–brown
crystals. The molecular structure (Fig. 3, Table 3)
comprises a quadrilateral Ru4 cluster [Ru–Ru 2.8218–
with a bite angle of 83.63(5)°. The H atom bridges the two
Ru atoms [Ru(1,3)–H 1.74, 1.85(5) A] which are chelatedto
ꢀ
the tertiary bis(phosphine) and r-bonded by the dehydr-
ophenyl group, respectively. With six Ru–Ru bonds, the
c.v.e. count is 60.
ꢀ
2.9420(4) A], to one side of which is attached a l4-C6H4

M.I. Bruce et al. / Inorganica Chimica Acta 357 (2004) 1805–1812
1807
group, while the other side supports the l4-P(nap)PPh2
phosphino–phosphinidene ligand. The benzyne ligand is
bent across the Ru4 cluster such that the C6-ring and
C(01,02)Ru(2,3) groups are approximately coplanar.
Bond distances indicate that atoms C(01,06) and
C(02,03) are bonded via g1:g2 interactions with Ru(2,1)
and Ru(3,4), respectively [Ru(2)–C(01) 2.111(2), Ru(3)–
C(02) 2.105(3); Ru(1)–C(01,06) 2.270, 2.533(2); Ru(4)–
2
ꢀ
C(02,03) 2.302, 2.577(3) A]; the g interactions are
highly asymmetric, with unusually long separations of
C(06,03) from Ru(1,4).
03
02
(OC)2
Ru4
Ru3(CO)3
Ru2(CO)3
06
01
OC
(OC)Ru1
P2
Ph2P1
108
101
(4)
Atom P(2) is attached to all four Ru atoms, being
ꢀ
nearer to Ru(2,3) [Ru–P 2.3582, 2.4075(7) A] than to
ꢀ
Ru(1,4) [Ru–P 2.4221, 2.4259(7) A], i.e. consistent with
the bonding pattern of the C6H4 group. Atom P(1) is
ꢀ
attached to Ru(1) [2.2862(6) A], with a chelate bite angle
P(1)–Ru(1)–P(2) of 85.71(2)°. Coordination is com-
pleted by ten CO ligands, one of which bridges the
Ru(1)–Ru(4) vector. The other nine are distributed three
each to Ru(2,3), two on Ru(4) and one on Ru(1). The
c.v.e. is 64, as predicted for an M4 cluster with only four
M–M bonds.
The reaction between dppn and Ru3(l-dppm)(CO)10
in refluxing thf produced several complexes, but apart
from Ru3{l3-PPhCH2PPh(C6H4)}(CO)9 (a known
thermal decomposition product of the starting cluster
[8]), the only tractable product was Ru3(l-dppm)-
(CO)8(dppn) (5), isolated in small yield. The X-ray
structural study showed that a simple substitution of
two CO groups on the Ru atom not bonded to the dppm
ligand had occurred. As shown in Fig. 4 and Table 4, all
P atoms occupy equatorial positions of an Ru3 cluster in
Fig. 1. Molecular projections of (a) Ru3(l-H){l3-PPh2(nap)PPh
(C6H4)}(CO)8 (1) and (b) Ru4(l-H){l3-PPh2(nap)PPh(C6H4)}(l-CO)3
(CO)7 (2), oblique to their Ru3 planes.
(OC)3
Ph2
Ru1
Ph2P1
Ph2P2
P3
101
Ru3
(CO)2
ꢀ
which the Ru–Ru separations [2.8703–2.9191(5) A] ap-
pear not to be related to the nature of any of the sub-
stituents. In comparison with the structure of the
P4
Ph2
108
Ru2
(OC)3
(5)
ꢀ
precursor, Ru(1)–Ru(2) [2.8703(6) A], bridged by the
dppm ligand, is of similar length. Chelation of Ru(3) by
ꢀ
the dppn ligand [Ru(3)–P(3,4) 2.284, 2.274(1) A] results
in shorter Ru–P distances than found for the edge-
ꢀ
bridging dppm [Ru–P 2.308, 2.324(1) A], as expected
The naphthyl group is commonly regarded as a rel-
atively rigid platform for substituents. The free dppn
ligand shows considerable distortion as a result of inter-
phenyl group contacts [1]. In the present series of
from its bite angle of 89.62(4)°.

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M.I. Bruce et al. / Inorganica Chimica Acta 357 (2004) 1805–1812
Table 1
Selected interatomic distances (A) (1, 2)
ꢀ
Atoms
Distance
2.8158(5), 2.8129(6)
Atoms
Distance
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(2)–C(111)
Ru(1)–H
Ru(1)–P(1)
Ru(1)–P(2)
Ru(2)–C(112)
Ru(3)–C(112)
Ru(3)–H
2.296(1), 2.320(1)
2.308(1), 2.341(1)
2.323(4), 2.302(5)
2.120(4), 2.120(5)
1.76(5), 1.85(5)
2.9926(4), 2.9361(6)
2.7078(5), 2.8238(7)
2.411(4), 2.314(5)
1.80(5), 1.74(5)
P(1)–C(101)
P(1)–C(111)
P(1)–C(121)
C(111)–C(112)
Ru(1)–C(11)
Ru(1)–C(12)
Ru(3)–C(31)
Ru(3)–C(32)
1.832(4), 1.823(5)
1.802(4), 1.789(5)
1.812(4), 1.826(5)
1.436(6), 1.423(7)
1.907(4), 1.927(5)
1.876(4), 1.879(5)
1.932(4), 1.948(5)
1.897(4), 1.925(6)
P(2)–C(108)
P(2)–C(211)
P(2)–C(221)
Ru(2)–C(21)
Ru(2)–C(22)
Ru(2)–C(23)
Ru(3)–C(33)
1.815(4), 1.822(5)
1.822(4), 1.819(5)
1.819(4), 1.814(5)
1.868(4), 2.095(6)
1.892(5), 1.877(6)
1.889(5), 1.861(6)
1.887(4), 1.878(6)
ꢀ
In 2, Ru(4)–Ru(1,2,3),C(41,42) are: 2.8836(8), 2.7128(6), 2.7493(7), 1.870(6), 1.834(6) A. Ru(4). . .C(11,21,31) are 2.569(5), 1.949(6), 2.666(5) with
associated Ru(n1)–C(n1)–O(n1) 161.7(5), 135.9(5), 164.0(5)°. Ru(4)–C(21)–O(21) is 139.9(5)°.
Fig.
PPh(nap)PPh2}(CO)11 (3), normal to the Ru3 plane.
2.
Molecular
projection
of
Ru4(l-H)(l3-C6H4){l-
Fig. 3. Molecular projection of Ru4{l4-P(nap)PPh2}(l4-C6H4)(l-
CO)(CO)9 (4), oblique to the Ru4 plane.
Table 2
Selected interatomic distances (A) (3)
ꢀ
Atoms
Distance
Atoms
Distance
Ru(1)–Ru(2)
Ru(2)–Ru(3)
Ru(2)–Ru(4)
Ru(3)–Ru(4)
Ru(4)–C(01)
Ru(4)–C(02)
P(1)–C(101)
P(1)–C(111)
P(1)–C(121)
C(01)–C(02)
Ru(1)–C(12)
Ru(2)–C(21)
Ru(2)–C(22)
Ru(4)–C(41)
Ru(4)–C(42)
2.8705(4)
3.0014(4)
2.7498(4)
2.7133(4)
2.297(3)
2.245(3)
1.846(3)
1.818(4)
1.837(3)
1.414(5)
1.953(3)
1.942(4)
1.882(3)
1.884(4)
1.928(4)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(2)–P(2)
Ru(2)–C(02)
Ru(3)–C(01)
Ru(2)–H
2.3092(8)
2.3377(8)
2.3287(8)
2.108(3)
2.088(3)
1.73(4)
complexes, the geometries of the dppn and dppn-derived
ligands, while showing consistent chelating behaviour
towards one ruthenium atom, are also involved in other
interactions. The extent to which the resulting distor-
tions (see Table 5) can be attributed to coordination is
debatable. Thus, the ‘bite’ distance of the ligand varies
Ru(3)–H
1.77(4)
P(2)–C(108)
P(2)–C(211)
Ru(1)–C(11)
Ru(1)–C(13)
Ru(3)–C(31)
Ru(3)–C(32)
Ru(3)–C(33)
Ru(4)–C(43)
1.812(3)
1.828(3)
1.942(3)
1.943(3)
1.948(4)
1.914(4)
1.902(4)
1.890(4)
ꢀ
by more than 0.1 A, supporting ‘bite’ angles which vary
by up to 6°. The associated P–C(nap) distances vary by
up to 0.05 A, which in turn impact on ring angles
(particularly exocyclic). Defining atom deviations of the
ꢀ
ꢀ
C10 ring planes approach up to 0.1 A in most of the
structures. Considerable deviations are also found for
the P atoms and the chelated Ru, which may occur ei-
ther side of the ring plane.
The C6 plane has a dihedral angle of 66.28(9)° to the Ru3 plane.
Ru(1) lies 0.878(2) A out of the latter.
ꢀ

M.I. Bruce et al. / Inorganica Chimica Acta 357 (2004) 1805–1812
1809
Table 3
Selected interatomic distances (A) (4)
vation of the dppn by coordination to the Ru3 cluster,
along with the presence of readily accessible coordination
sites (by loss of CO), then results in (a) aryl C–H bond
cleavage to give (aryl+ H), as in 1 and 2, followed by (b)
aryl C–P bond cleavage (to give C6H4 + phosphide), as in
3. A third reaction involves loss of benzene by combination
of (H + Ph) to give phosphinidene, as in 4. It is not possible
to say whether aryl C–P bond cleavage to give Ph occurs
before the aryl C–H cleavage. Cluster-bonded Ph groups
are rare, either elimination as benzene or further degra-
dation to benzyne on the cluster occurring (see Table 6).
There do not appear to be any other structurally
characterised examples of Ru3 carbonyl clusters in
which one edge is bridged by a bidentate phosphine and
the third metal atom is chelated by the same or a dif-
ferent phosphine. The nearest analogues in the Cam-
bridge Data Base are examples where a monodentate
phosphine is attached to the third metal atom, such
as Ru3(l-dppm)(CO)9(PR3) [PR3 ¼ P(OMe)3 [9], PPh2-
(C6H4N@CHPh-2) [10], PPh2{C6H4NHC(O)Ph-2}
[11], PPh2(C6H4CHO-2) [11] and Ru3{l-(PPh2)2-C ¼
CH2}(CO)9{PPh2CH2CH[(PPh2)2Fe(CO)3]} [12]].
ꢀ
Atoms
Distance
Atoms
Distance
Ru(1)–Ru(2)
Ru(1)–Ru(4)
Ru(2)–Ru(3)
Ru(3)–Ru(4)
C(01)–C(02)
C(01)–Ru(1)
C(01)–Ru(2)
Ru(1)–C(06)
Ru(4)–C(03)
Ru(1)–C(11)
Ru(1)–C(12)
Ru(2)–C(21)
Ru(2)–C(22)
Ru(2)–C(23)
Ru(4)–C(12)
P(2)–C(108)
2.9010(4)
2.8218(4)
2.9420(4)
2.8912(4)
1.445(4)
2.270(2)
2.111(2)
2.533(2)
2.577(3)
1.873(3)
2.017(3)
1.961(3)
1.897(3)
1.927(3)
2.090(3)
1.826(3)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(2)–P(2)
Ru(3)–P(2)
Ru(4)–P(2)
C(02)–Ru(3)
C(02)–Ru(4)
Ru(3)–C(31)
Ru(3)–C(32)
Ru(3)–C(33)
Ru(4)–C(41)
Ru(4)–C(42)
P(1)–C(101)
P(1)–C(111)
P(1)–C(121)
2.2862(6)
2.4221(8)
2.3582(7)
2.4075(6)
2.4259(7)
2.105(3)
2.302(3)
1.936(5)
1.903(3)
1.916(2)
1.873(3)
1.897(3)
1.817(3)
1.824(3)
1.834(3)
The Ru4/C6 interplanar dihedral angle is 74.07(3)°; P(2) lies
1.265(1) A out of the Ru4 plane.
ꢀ
3. Conclusions
This preliminary study of the reactions of the steri-
cally demanding dppn ligand with trinuclear ruthenium
carbonyl clusters has shown that the close separation of
the two phosphorus atoms in the bis(tertiary phosphine)
results in exclusive chelation to one metal centre, as
expected. The marked tendency for C–H and P–C bond
cleavage reactions found with phosphine-substituted
ruthenium and osmium cluster carbonyls, usually upon
heating [13], is also evident here. Under relatively mild
conditions (refluxing thf), complexes containing ortho-
metallated phenyl or benzyne ligands are formed by C–
H and C–P bond cleavage, respectively.
Fig. 4. Molecular projection of Ru3(l-dppm)(CO)8(dppn) (5), normal
to the Ru3 plane.
Coordination of the P–C6H4 ligand is found in the
g1:g2 mode, while in the two benzyne-containing clus-
ters, examples of l3-g1:g1:g2-(as a four-electron donor
in 3) and l4-g1:g1;g2:g2-bonding modes (as a six-elec-
tron donor in 4) have been characterised. These have
precedents in several thermal decomposition (alteration)
products from phosphine-containing Ru3 and Os3
clusters [14] and, more recently, in studies of C6H4 on Ir
{1 0 0} surfaces. In the latter, the plane of the di-r-
bonded benzyne ring is tilted at 47.2° to the surface
normal [15]. In 3 and 4, corresponding angles are
66.28(9) and 49.35(7)°, respectively, and are consistent
with the bonding modes mentioned above. Alterna-
tively, theoretical studies of the surface-adsorbed species
have concluded that the tilt arises from back-bonding of
the C6 p-system to the metal d orbitals [16].
Table 4
Selected interatomic distances (A) (5)
ꢀ
Atoms
Distance
Atoms
Distance
Ru(1)–P(1)
Ru(2)–P(2)
Ru(3)–P(3)
Ru(3)–P(4)
Ru(1)–Ru(2)
Ru(1)–Ru(3)
2.308(1)
2.324(1)
2.284(1)
2.274(1)
2.8703(6)
2.8841(5)
P(1)–C(0)
P(2)–C(0)
1.860(4)
1.859(4)
1.860(4)
1.854(4)
2.9191(5)
P(3)–C(101)
P(4)–C(108)
Ru(2)–Ru(3)
Ru(n)–P(n)–C(0)(n ¼ 1,2) are 112.7(1), 115.0(1); Ru(3)–P(3)–
C(101), Ru(3)–P(4)–C(108) are 117.7(1), 114.4(1)°.
It is likely that the first-formed complex in the reaction
of dppn with Ru3(CO)12 is a simple chelate complex,
Ru3(CO)10(dppn), as found in the formation of 5. Acti-
In the present work, we have not been able to isolate
any complexes in which the C10 group interacts with the

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M.I. Bruce et al. / Inorganica Chimica Acta 357 (2004) 1805–1812
Table 5
Naphthyl chelate descriptors
Atoms
1
2
3
4
5a
Lb
ꢀ
Distances (A)
P. . .P
3.094(1)
1.832(4)
1.815(4)
3.107(2)
1.823(5)
1.822(5)
3.177(1)
1.846(3)
1.812(3)
3.2040(9)
1.817(3)
1.826(3)
3.118(1)
1.860(4)
1.854(4)
3.0483(6)
1.851(2)
1.840(2)
P–C(101)
P–C(108)
Angles (degrees)
P–Ru–P
Ru–P–C(101)
84.43(3)
117.0(1)
111.2(1)
114.2(3)
118.1(3)
125.9(3)
122.1(3)
83.63(5)
113.4(2)
120.3(2)
117.7(4)
115.0(4)
122.2(4)
125.2(4)
86.27(3)
113.8(1)
111.5(1)
115.2(2)
114.6(2)
126.1(2)
124.8(2)
85.71(2)
119.96(7)
120.86(9)
117.6(2)
115.3(2)
121.2(2)
125.1(2)
89.62(4)
117.7(1)
114.4(1)
113.6(3)
117.2(3)
126.8(3)
123.7(3)
Ru–P–C(108)
P–C(101)–C(102)
P–C(108)–C(107)
P–C(101)–C(108a)
P–C(108)–C(108a)
117.6(2)
118.0(1)
124.1(1)
122.2(2)
Torsion angles (degrees)
P(2)–Ru–P(1)–C(101)
41.31(1)
)12.4(4)
)14.3(5)
)8.3(5)
53.5(3)
53.2(2)
)55.2(4)
10.1(7)
17.8(8)
2.9(5)
)47.3(1)
27.3(3)
3.3(5)
)37.6(1)
56.2(2)
)20.6(3)
)20.7(4)
24.9(3)
5.3(1)
)32.6(2)
7.8(4)
Ru–P(1)–C(101)–C(108a)
P(1)–C(101)–C(108a)–C(108)
C(101)–C(108a)–C(108)–P(2)
C(108a)–C(108)–P(2)–Ru
C(108)–P(2)–Ru–P(1)
13.1(6)
6.2(6)
)8.0(2)
)12.8(2)
6.2(5)
)43.8(3)
54.2(1)
)43.4(4)
46.5(2)
)57.4(1)
)33.3(2)
ꢀ
C10 plane parameters (deviations, d; in A)
v2(plane)
dP(1)
dP(2)
1131
1331
1871
0.706(3)
1214
10679
0.333(2)
)0.474(2)
0.438(4)
)0.331(4)
1.242(5)
58.60(7)
0.437(5)
)0.508(6)
)1.070(8)
0.377(4)
)0.301(4)
0.970(6)
34.56(8)
)0.586(3)
)0.324(4)
70.07(5) [Ru4]
dRu
C
10/Ru3 dihedral (°)
Across the six compounds, mean values are: Distances C(101)–C(102), C(107)–C(108) 1.380(8), 1.378(4); C(102)–C(103), C(106)–C(107) 1.402(5),
1.404(10); C(103)–C(104), C(105)–C(106) 1.353(13), 1.353(12); C(104a)–C(104, 105) 1.410(10), 1.415(7); C(104a)–C(108a) 1.436(6); C(108a)–C(101,
ꢀ
108) 1.439(11), 1.440(11) A. Angles C(108a)–C(101)–C(102), C(108a)–C(108)–C(107) 119.2(6), 119.4(6); C(101)–C(102)–C(103), C(106)–C(107)–
C(108) 122.8(7), 122.5(7); C(102)–C(103)–C(104), C(105)–C(106)–C(107) 119.0(5), 119.4(4); C(104a)–C(104)–C(103), C(104a)–C(105)–C(106)
121.2(8), 121.0(5); C(108a)–C(104a)–C(104, 105) 120.6(6), 120.5(6); C(104a)–C(108a)–C(101, 108) 116.8(2), 116.9(5); C(101)–C(108a)–C(108)
126.4(6); C(104)–C(104a)–C(105) 118.9(12)°.
a For P(1,2) read P(3,4).
b Ref. [1].
clusters, no doubt because of the more easily cleaved P–
Ph bonds in dppn. Studies of similar reactions with 1,8-
bis(dimethylphosphino)naphthalene are directed to the
incorporation of the naphthyl group on the cluster and
will be reported elsewhere.
windows. NMR spectra were recorded on Bruker
AM300WB or ACP300 (1H at 300.13 MHz, 31P NMR
at 121.50 MHz) or 600 Unity Nova (1H at 599.92 MHz)
instruments. Samples were dissolved in CDCl3 and
contained in 5 mm sample tubes. Chemical shifts are
given in ppm relative to internal tetramethysilane. Mass
spectra were recorded on a VG Platform 2 instrument.
Solutions were infused directly into the instrument.
Chemical aids to ionisation were used as required [17].
Elemental analyses were performed at the Centre for
Micro-analytical Services (CMAS), Belmont, Vic.
4. Experimental
4.1. General experimental conditions
All reactions were carried out under dry, high purity
nitrogen using standard Schlenk techniques. Common
solvents were dried, distilled under argon and degassed
before use.
4.3. Reagents
Ru3(CO)12 [18], Ru3(l-dppm)(CO)10 [19] and dppn
[1,20] were prepared by the cited methods.
4.2. Instrumentation
4.4. Reaction of Ru3(CO)12 with dppn in thf
Infrared spectra were obtained on a Bruker IFS28
FT-IR spectrometer. Spectra in CH2Cl2 were obtained
using a solution cell of 0.5 mm path-length with NaCl
A mixture of Ru3(CO)12 (40 mg, 0.063 mmol) and
dppn (31 mg, 0.062 mmol) in thf (12 ml) was heated at

M.I. Bruce et al. / Inorganica Chimica Acta 357 (2004) 1805–1812
1811
Table 6
Crystal data and refinement details
Compound
1
2
3
4
5
Formula
MW
C
42H26O8P2Ru3 ꢂ CH2Cl2 C44H26O10P2Ru4
C45H26O11P2Ru4 ꢂ CH2Cl2 C38H20O10P2Ru4
C67H48O8P4Ru3 ꢂ CH2Cl2
1493.15
monoclinic
1108.75
triclinic
1180.91
orthorhombic
1293.85
monoclinic
P21=n
1102.80
monoclinic
Crystal system
Space group
ꢁ
P1
Pccn
P21=n
P21=n
12.679(2)
ꢀ
a (A)
10.3090(9)
13.954(1)
15.020(1)
86.355(2)
85.653(2)
85.104(2)
2143
11.495(2)
35.788(5)
19.517(3)
17.547(1)
13.457(8)
19.198(1)
19.034(2)
9.533(1)
21.455(2)
ꢀ
b (A)
25.824(3)
18.863(2)
ꢀ
c (A)
a (°)
b (°)
c (°)
91.984(2)
113.273(3)
95.237(3)
3
ꢀ
V (A )
8029
4531
3576
6150
Z
2
1.717
8
1.954
4
1.897
4
2.048
4
1.612
Dc (g cmꢁ3
)
l (mmꢁ1
)
1.29
1.62
0.25 ꢃ 0.22 ꢃ 0.11
1.56
1.81
0.98
Crystal size (mm) 0.24 ꢃ 0.22 ꢃ 0.09
0.30 ꢃ 0.24 ꢃ 0.16
0.81
65
0.44 ꢃ 0.28 ꢃ 0.26
0.81
75
0.38 ꢃ 0.14 ꢃ 0.12
0.90
58
‘T’min=max
2hmax (°)
Ntot
0.85
70
0.80
55
39,584
18,766 (0.033)
9216
80,360
9234 (0.075)
7090
73,008
16,507 (0.047)
12,637
0.042
47,439
18,805 (0.037)
14,254
0.040
74,744
16,165 (0.067)
12,085
0.047
N (Rint
No
R
)
0.039
0.052
0.043
0.054
Rw
0.045
0.048
0.064
reflux point for 5.5 h. After evaporation to dryness
(rotary evaporator), preparative t.l.c. (acetone/hexane,
3/7) separated three major products. Band 1 (orange, Rf
0.56) afforded Ru3(l-H){l3-Ph2P(nap)PPhC6H4}(CO)8
(1) (16.4 mg, 26%) as red crystals from CH2Cl2/hexane.
Anal. Calc. C42H26O8P2Ru3: C, 49.27; H, 2.56. Found:
C, 49.30; H, 2.60%. M, 1025. IR (CH2Cl2): m(CO) 2063s,
(m, 25H, Ph + nap + C6H4). ES-MS (positive ion,
MeOH, m=z): 1182, Mþ; (+ve ion, MeOH + NaOMe,
m=z): 1205, [M + Na]þ; (negative ion, MeOH, m/z):
1212, [M + OMe]ꢁ. Other bands contained trace
amounts of unidentified products.
4.5. Reaction of Ru3(CO)12 with dppn in toluene
2023vs, 2003s, 1992(sh), 1966m, 1948(sh) cmꢁ1 1H
.
NMR: d-17.11 [d of d, 1H, J(PH) 20.4, 12.9 Hz, Ru–H],
6.36–8.03 (m, 25H, Ph + nap + C6H4). ES-MS (positive
ion, MeOH, m=z): 1025, [M]þ; (+ve ion, MeOH + Na-
OMe, m=z): 1048, [M + Na]þ; (negative ion,
MeOH + NaOMe): 1056, [M + OMe]ꢁ. Band 2 (orange–
yellow, Rf 0.50) afforded Ru4(l-H)(l3-C6H4){l-
Ph2P(nap)PPh}(CO)11. CH2Cl2 (3) as bright orange
crystals (9.1 mg, 12%) from CH2Cl2/MeOH. Anal. Calc.
C45H26O11P2Ru4 ꢂ CH2Cl2: C, 42.70; H, 2.18. Found: C,
42.67; H, 2.20%. M, 1210. IR (CH2Cl2): m(CO) 2082w,
2057m, 2029vs, 2014m, 1993w, 1983m, 1977(sh), 1929w
cmꢁ1. 1H NMR: d-21.26 [d of d, 1H, J(PH) 12.3, 1.8 Hz,
RuH), 5.30 (s, 2H, CH2Cl2), 6.26–8.07 (m, 25H,
Ph + nap + C6H4). ES-MS (positive ion, MeOH + Na-
OMe, m=z): 1233, [M + Na]þ; 1210, Mþ; 1177,
[M + Na)2CO]þ; 1154, [M–2CO]þ. Band 3 (brown, Rf
0.42) contained Ru4(l-H){l3-Ph2P(nap)PPh(C6H4)}
(l-CO)3(CO)7 (2) (7.0 mg, 10%) as dark brown–black
crystals from CH2Cl2/MeOH. Anal. Calc. C44H26-
O10P2Ru4: C, 44.75; H, 2.20. Found: C, 44.62; H 2.15%.
M, 1182. IR (CH2Cl2): m(CO) 2062m, 2025vs, 2001vs,
Preparative t.l.c. (acetone/hexane, 1/2) of a similar
reaction between Ru3(CO)12 (50 mg, 0.078 mmol) and
dppn (39 mg, 0.079 mmol) in refluxing toluene (18 ml)
gave an orange band at Rf 0.72 which was crystallized
from CH2Cl2/hexane to give orange–brown crystals
of Ru4{l4-P(nap)PPh2}(l4-C6H4)(l-CO)(CO)9 (4) (4.2
mg, 5%). The small amount of this complex precluded
an elemental analysis and it was characterised by the X-
ray study. IR m(CO) (CH2Cl2) 2073s, 2036vs, 2014vs,
1981m, 1877w(br), 1771w(br) cmꢁ1. ES-MS (positive
ion, MeOH + NaOMe, m=z): 1127, [M + Na]þ (C38H20-
O10P2Ru4 Calc.: M, 1104).
4.6. Reaction of Ru3(l-dppm)(CO)10 with dppn
A mixture of Ru3(l-dppm)(CO)10 (80 mg, 0.083
mmol) and dppn (41 mg, 0.083 mmol) in thf (16 ml) was
heated at reflux for 6.5 h. After evaporation to dryness
preparative t.l.c. (acetone/hexane, 1/2) showed a number
of bands. Band 1 (red, Rf 0.32) was crystallised from
CH2Cl2/hexane to give Ru3(l-dppm)(CO)8(dppn).
CH2Cl2 (5) (10 mg, 9%) as red needles. Drying
1
1989(sh), 1959w, 1939w, 1769w (br) cmꢁ1. H NMR: d-
17.57 [d of d, 1H, J(PH) 22.8, 8.7 Hz, Ru–H], 6.16–8.05

1812
M.I. Bruce et al. / Inorganica Chimica Acta 357 (2004) 1805–1812
under vacuum removed the CH2Cl2 from the analytical
sample. Anal. Calc. C67H48O8P4Ru3: C, 57.15; H, 3.44.
Found: C, 56.70; H, 3.57%. M, 1409. IR (CH2Cl2):
m(CO) 2028vw, 1979vs, 1953vs (br), 1932(sh), 1903 (sh)
cmꢁ1. 1H NMR: d 4.04 [t, 2H, J(PH) 10Hz, CH2], 6.98–
7.40 and 7.97–7.99 (m, 46H, Ph + nap). 31P NMR: d
15.98 (s, dppm), 35.97 (s, dppn). ES-MS (positive ion,
MeOH, m=z): 1409, Mþ.
Acknowledgements
We thank the Australian Research Council for sup-
port of this work and Johnson-Matthey plc, Reading,
UK, for a generous loan of RuCl3 ꢂ nH2O.
References
Bands 2 (orange–yellow, Rf 0.47) and 3 (pale orange,
Rf 0.57) contained Ru3(l-dppm)(CO)10 (23.6 mg, 29.5%)
and Ru3{l3-PPhCH2PPh(C6H4)}(CO)9 (1.6 mg, 2%),
respectively, both identified by comparison of their
m(CO) IR spectrum (cyclohexane) with those of au-
thentic samples.
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ꢄ153 K using a Bruker AXS CCD area-detector in-
strument. Ntot reflections were merged to N unique (Rint
cited) after ‘‘empirical’’/multiscan absorption correction
(proprietary software), No with F > 4rðF Þ being used in
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ꢀ
k ¼ 0:71073 A. Anisotropic displacement parameter
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(x; y; z; UisoÞH being constrained at estimates. Conven-
tional residuals R, Rw on jF j are quoted [weights:
(r2ðF Þ þ 0:0004F 2Þꢁ1ꢅ. Neutral atom complex scattering
factors were used; computation used the XTAL 3.7
program system [21]. Pertinent results are given in the
figures (which show non-hydrogen atoms with 50%
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I.A. Razak, Acta Crystallogr. C 54 (1998) 329.
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[12] P.A. Dolby, M.M. Harding, N. Nawar, A.K. Smith, J. Chem. Soc.
Dalton Trans. (1992) 2939.
ꢀ
hydrogen atoms with arbitrary radii of 0.1 A) and
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(b) W.R. Cullen, Adv. Inorg. Chem. Radiochem. 15 (1972) 323;
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4.8. Variata
[14] (a) W.R. Cullen, S.T. Chacon, M.I. Bruce, F.W.B. Einstein, R.H.
Jones, Organometallics 7 (1988) 2273;
1–3. The cluster-bound hydrogens were located and
refined in (x; y; z; Uiso). The solvent molecules in 1 and 3
were modelled as disordered over two sites, occupan-
cies set at 0.5 after trial refinement, with constrained
geometries.
(b) A.J. Deeming, Adv. Organomet. Chem. 26 (1986) 1;
(c) M.I. Bruce, P.A. Humphrey, O. bin Shawkataly, M.R. Snow,
E.R.T. Tiekink, W.R. Cullen, Organometallics 9 (1990) 2910.
[15] K. Johnson, B. Sauerhammer, S. Titmuss, D.A. King, J. Chem.
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4. All hydrogen atoms were refined in (x; y; z; Uiso).
[16] S. Yamagishi, S.J. Jenkins, D.A. King, J. Chem. Phys. 117 (2002)
819.
[17] W. Henderson, J.S. McIndoe, B.K. Nicholson, P.J. Dyson, J.
Chem. Soc. Dalton Trans. (1998) 519.
4.9. Supplementary material
[18] M.I. Bruce, C.M. Jensen, N.L. Jones, Inorg. Synth. 28 (1990) 216.
[19] M.I. Bruce, B.K. Nicholson, M.L. Williams, Inorg. Synth. 28
(1990) 225.
Full details of the structure determinations of com-
plexes 1–5 (except structure factors) have been deposited
with the Cambridge Crystallographic Data Centre as
CCDC 219944-219948, respectively. Copies of this in-
formation may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (fax: +44-1223-336-033; e-mail: deposit@ccdc.
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
€
[20] (a) A. Karaßcar, H. Thonnessen, P.G. Jones, R. Bartsch, R.
Schmutzler, Heteroat. Chem. 8 (1997) 539;
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[21] S.R. Hall, D.J. du Boulay, R. Olthof-Hazekamp (Eds.), The
XTAL 3.7 System, University of Western Australia, Perth, 2000.