Vinylidene complexes of osmium(0) derived from 1-naphthyl- or 2-naphthyl-carbyne complexes by hydride addition to the naphthyl substituents. The crystal structure of Os(=C=C10H8)(CO)2(PPh3)2

Article abstract of DOI:10.1016/S0022-328X(98)00451-3

When treated with lithium triethylborohydride, the cationic carbyne complexes [Os(-CR)(CO)₂(PPh₃)₂]⁺(R=1-naphthyl, 1; R=2-naphthyl, 2) form 3 and 4, respectively, which both have the formula Os(C₁₁H

Full text of DOI:10.1016/S0022-328X(98)00451-3

Journal of Organometallic Chemistry 565 (1998) 153–158
Vinylidene complexes of osmium(0) derived from 1-naphthyl- or
2-naphthyl-carbyne complexes by hydride addition to the naphthyl
1
substituents. The crystal structure of Os(ꢀCꢀC10H8)(CO)2(PPh3)2
Lisa-J. Baker, Clifton E.F. Rickard, Warren R. Roper *, Scott D. Woodgate, L. James Wright
Department of Chemistry, The Uni6ersity of Auckland, Pri6ate Bag 92019, Auckland, New Zealand
Received 3 December 1997
Abstract
When treated with lithium triethylborohydride, the cationic carbyne complexes [Os(–CR)(CO)2(PPh3)2]+(R=1-naphthyl, 1;
R=2-naphthyl, 2) form 3 and 4, respectively, which both have the formula Os(C11H8)(CO)2(PPh3)2. NMR studies of these two
isomeric vinylidene complexes show that the product derived from the 1-naphthyl carbyne cation involves attack at the naphthyl
ring in the position para to the carbyne carbon to give 3, while that derived from the 2-naphthyl carbyne cation involves attack
at the naphthyl ring in the position ortho to the carbyne carbon to give 4. The structure of 4 has been confirmed by an X-ray
crystal structure determination. Addition of HCl to the vinylidene complexes 3 or 4 results in the formation of the corresponding
naphthylmethyl complexes, Os(CH2R)Cl(CO)2(PPh3)2 (R=1-naphthyl, 5; R=2-naphthyl, 6). © 1998 Elsevier Science S.A. All
rights reserved.
Keywords: Naphthyl substituents; Hydride addition; Vinylidene complexes; Osmium(0)
1. Introduction
The electrophilicity of the carbyne carbon in cationic
carbyne complexes is well established [1] and a recent
example is shown in Eq. 1 [2].
The explanation for the unexpected position of at-
tack probably lies with the superior y-acceptor proper-
ties of the vinylidene ligand compared with the carbene
ligand that would otherwise result from direct attack at
C(carbyne) [4].
With the recent availability of [Os(–CR)(CO)2
(PPh3)2]+ClO4− (R=1-naphthyl, 1; R=2-naphthyl, 2)
[5], we have investigated this reaction further because
in these complexes there are a greater number of
potential sites for hydride attack and, indeed, it is
not possible for hydride to attack the para-position
of a 2-naphthyl system as this is a bridgehead
carbon. The possibility remained that here the
hydride attack might occur at the carbyne carbon
atom.
However, in a quite unexpected reaction, we have
shown that [Os(–C-p-tolyl)(CO)2(PPh3)2]+ClO4−, when
treated with LiEt3BH, forms an unusual vinylidene
complex of formula Os(C8H8)(CO)2(PPh3)2 which re-
sults from hydride attack at the tolyl ring in the para-
position (Eq. 2) [3].
* Corresponding author. Tel.: +64 9 373799; fax: +64 9 3737422.
1 Dedicated to Professor Michael Bruce on the occasion of his 60th
birthday.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00451-3

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L.-J. Baker et al. / Journal of Organometallic Chemistry 565 (1998) 153–158
2. Results and discussion
The addition of LiEt3BH to THF solutions contain-
ing either of the dark red complexes [Os(–
CR)(CO)2(PPh3)2]+ClO4−
(R=1-naphthyl,
1;
R=2-naphthyl, 2) gives almost colourless solutions
from which the corresponding pale yellow crystalline
complexes, 3 or 4, can be isolated. Elemental analyses
and high-resolution mass spectra indicated that both 3
and 4 have the formula Os(C11H8)(CO)2(PPh3)2, consis-
tent with addition of a single hydride to each of the
1
precursor complexes, 1 or 2. In the H-NMR spectrum
of each compound, no high-field signals (lB0 ppm)
were observed which ruled out the possibility of os-
mium hydride formation and, in addition, no signals
were observed in the l 10–20 ppm region which
showed that no hydrogen-substituted carbene ligands
had been formed. Therefore, the most likely point of
attack appeared to be at the naphthyl substituents to
give vinylidene products, and indeed the w(CO) values
for 3 (1955, 1892 cm−1) and 4 (1957, 1894 cm−1) were
very close to values found (1956, 1897 cm−1) for the
previously reported vinylidene complex derived from
[Os(ꢁC-p-tolyl)(CO)2(PPh3)2]+ (Eq. 2) [3].
Scheme 2. The four possible vinylidene isomers (A–D) for complex
(4).
isomers that are consistent with these observations are
A and B (Scheme 1). Both of these isomers have four
aromatic protons (aromaticity is retained in at least one
ring), two vinyl protons and two methylene protons,
but they differ in the location of the methylene group.
In order to distinguish between these two isomers, the
13C-NMR spectrum of 3 was obtained. For isomer B it
would be expected that the methylene carbon should
couple to the two phosphorus nuclei with a coupling
constant of about 7 Hz, as is seen in the product
derived from the 2-naphthylcarbyne cation (see below).
However, for isomer A the methylene carbon should
display very much smaller, or non-observable, coupling
to phosphorus in the 13C-NMR spectrum. In practice,
the 13C{1H}-NMR spectrum of 3 shows the methylene
carbon as a singlet at 25.3 ppm. This implies that
hydride attack occurs at the 4-position (see Scheme 3
for the numbering system used for the naphthyl rings in
3 and 4) of the naphthyl ring in 1 and that isomer A is
the correct formulation for compound 3. Hydride at-
tack occurred at an analogous position in the p-tolyl
carbyne complex shown in Eq. 2. The data from an
HMQC 13C{1H}-NMR spectrum were used to assign H
and C chemical shifts. Complete 1H- and 13C-NMR
spectral data are presented in the Section 3.
2.1. Formation of the 6inylidene complex 3 from
reaction between LiEt3BH and the 1-naphthyl carbyne
complex 1
There are four possible naphthyl ring positions in 1
at which hydride addition could occur to give vinyli-
dene products (Scheme 1). However, in practice only
one of the isomers (A–D) is formed.
The 1H-NMR of 3 shows two methylene protons at l
2.8 ppm, two vinyl protons at 4.8 and 5.7 ppm and four
1
aromatic protons at 6.7–6.9 ppm. A COSY H{1H}-
NMR spectrum shows that the aromatic protons cou-
ple only with each other, whereas the two vinyl protons
couple with each other and the methylene protons. Two
2.2. Formation of the 6inylidene complex 4 through
reaction between LiEt3BH and the 2-naphthyl
carbyne-containing complex 2
As with compound 1, there are four possible naph-
thyl ring positions in 2 at which hydride addition could
occur to give vinylidene products (Scheme 2). One
important difference between compounds 2 and 1 is
that attack at the position para to the carbyne carbon
in 2 (C10, Scheme 3) is not possible as this is a
bridgehead carbon atom.
1
The H-NMR spectrum of 4 revealed three distinctly
different types of protons; two methylene protons at l
2.9 ppm, two vinyl protons at 5.3–5.6 ppm and four
aromatic protons at 6.5–7.0 ppm. A 1H{1H} COSY
Scheme 1. The four possible vinylidene isomers (A–D) for complex
(3).

L.-J. Baker et al. / Journal of Organometallic Chemistry 565 (1998) 153–158
155
experiment showed that the two equivalent methylene
protons did not couple with any other protons, the two
vinyl protons only coupled with each other, and the
aromatic protons coupled with each other, but no other
protons. Isomer D (Scheme 2) is the only isomer consis-
1
tent with all the H-NMR data.
1
Although a H{1H} homonuclear decoupling NMR
experiment confirmed that the methylene protons did
not couple with any other protons, the signal at l 2.9
ppm appeared as a triplet with a coupling constant of
7.7 Hz. This signal did collapse to a singlet, however, in
the 31P-decoupled 1H-NMR spectrum of 4, showing
that coupling to two equivalent phosphorus nuclei was
responsible for the multiplicity of the methylene signal.
The other protons in the same ring as the methylene
group show much smaller coupling (1.7 and 2.7 Hz) to
the two phosphorus nuclei.
The results of an HMQC 13C{1H}-NMR experiment
enabled chemical shift assignments to be made for the
atoms of the vinylidene group in this complex. The
assignments listed in Section 3 should be read in con-
junction with the numbering scheme given in Scheme 3.
The 13C-NMR spectrum showed that even for carbon
atoms up to six bonds away from the phosphorus
atoms, coupling to these nuclei was still discernible.
The vinylidene-carbon in 4 appears at the very lowfi-
eld position of l 295.7 ppm in the 13C-NMR spectrum.
This is upfield from the carbyne carbon resonance of
Fig. 1. Molecular structure of Os(C11H8)(CO)2(PPh3)2 (4) showing
the atom numbering scheme. Thermal ellipsoids are at the 30%
probability level.
plane defined by the other ring carbon atoms (C(2)–
C(10)), and the distances between C(1) and the neigh-
˚
bouring carbon atoms, C(2) (1.518(12) A) and C(9)
˚
(1.562(12) A), are consistent with there being only
single bonds to these atoms. This confirms that the
methylene group is at C(1). The short distance between
˚
C(3) and C(4) (1.339(12) A) suggests that there is
the
precursor
compound,
[Os(ꢁC-2-naph-
significant double bond character between these two
thyl)(CO)2(PPh3)2]+ClO4− (1), which appears at 331.8
ppm, but is very similar in position to the carbene
carbon resonance in the complex Os[ꢀCH(2-naph-
thyl)]Cl2(CO)(PPh3)2 which appears at 291.3 ppm [5].
A single crystal X-ray structure determination of the
complex Os(C11H8)(CO)2(PPh3)2 (4) confirmed the
vinylidene (isomer D, Scheme 2) formulation. The OR-
TEP diagram is depicted in Fig. 1. Crystal data and
structure refinement parameters, final atomic coordi-
nates, and selected bond distances and angles are given
in Tables 1–3, respectively. The coordination geometry
about osmium is approximately trigonal bipyramidal
with the two triphenylphosphine ligands in the axial
positions. The vinylidene and the two carbonyl ligands
are in the equatorial positions with the rings of the
vinylidene substituent essentially in the equatorial
plane. The hydrogen atoms were not located, but it can
be clearly seen that hydride addition occurred at C(1).
˚
atoms and a similar distance (1.356(11) A) is found
between C(2) and the vinylidene carbon atom, C(11).
˚
The Os–C(11) bond length of 1.900(8) A is the same as
the corresponding distance reported for the related
vinylidene complex shown in Eq. 2 [3]. Two other
osmium vinylidene complexes have been reported to
have very similar Os–C(vinylidene) bond lengths to
this, and both have carbonyl and cyclopentadienyl sup-
˚
porting ligands [6,7]. Shorter distances of ca. 1.81 A
have been reported for the Os–C(vinylidene) bond in
complexes that contain no y-acid supporting ligands
[8,9].
It is noteworthy that hydride attacks 2 at the most
sterically-protected ring carbon atom (C1) to give iso-
mer D (Scheme 3). However, this isomer is the only one
in which the aromaticity of both naphthyl rings is not
disrupted and this probably provides an important
driving force for hydride attack at this ring position.
No evidence for any hydride attack at the carbyne
carbon atom in 2 was obtained.
˚
This carbon atom is displaced by 0.337(11) A from the
2.3. Formation of the 1- and 2-naphthylmethyl
products 5 and 6 through HCl addition to 3 and 4
Addition of HCl to the vinylidene complexes, 3 or 4,
Scheme 3. Hydride attack of complex 2.
results in the formation of the corresponding naphthyl-

156
L.-J. Baker et al. / Journal of Organometallic Chemistry 565 (1998) 153–158
Table 2
methyl complexes 5 or 6 (Scheme 4) in good yield. A
similar reaction occurred on addition of HCl to the
vinylidene complex shown in Eq. 2 [3] to give a 4-methyl-
benzyl complex. The mechanism by which these rear-
rangements proceed is not clear, but the initial steps may
involve either direct addition of H+ to the vinylidene
carbon, or protonation of the osmium centre followed by
hydride migration to the vinylidene carbon atom.
Atomic coordinates and equivalent isotropic displacement parameters
for Os(C11H8)(CO)2(PPh3)2 (4)
Atom
x
y
z
U(eq)
Os(1)
P(1)
P(2)
O(1)
O(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
0.2716(1)
0.3068(2)
0.2835(2)
0.3327(7)
0.1952(1)
0.0880(1)
0.3094(1)
0.1152(3)
0.1951(3)
0.2714(6)
0.2710(4)
0.3112(5)
0.3379(5)
0.3458(5)
0.3303(5)
0.2959(6)
0.2741(5)
0.2890(5)
0.3260(4)
0.2376(4)
0.1455(4)
0.1923(4)
0.0060(4)
0.0891(1)
0.1436(1)
0.0437(1)
0.024(1)
0.025(1)
0.024(1)
0.054(2)
0.053(2)
0.057(3)
0.039(2)
0.046(2)
0.055(2)
0.057(3)
0.063(3)
0.062(3)
0.058(3)
0.047(2)
0.043(2)
0.036(2)
0.032(2)
0.034(2)
0.028(2)
0.068(3)
0.093(4)
0.061(3)
0.055(3)
0.046(2)
0.031(2)
0.055(3)
0.063(3)
0.055(3)
0.059(3)
0.042(2)
0.029(2)
0.044(2)
0.052(2)
0.076(3)
0.054(2)
0.057(3)
0.026(2)
0.044(2)
0.051(2)
0.053(2)
0.055(2)
0.039(2)
0.025(2)
0.039(2)
0.047(2)
0.044(2)
0.048(2)
0.039(2)
0.025(2)
0.033(2)
0.040(2)
0.035(2)
0.040(2)
0.034(2)
−0.0272(3)
0.0905(3)
0.1771(4)
0.1868(4)
0.2377(4)
0.2801(4)
0.3301(4)
0.3305(5)
0.2844(4)
0.2347(4)
0.2336(4)
0.2799(4)
0.1474(3)
0.0156(3)
0.0884(3)
0.1047(3)
0.0915(5)
0.0625(6)
0.0460(4)
0.0585(4)
0.0872(4)
0.1605(3)
0.1145(4)
0.1241(5)
0.1796(5)
0.2252(4)
0.2150(4)
0.2169(3)
0.2385(4)
0.2948(4)
0.3098(4)
0.3304(4)
0.2526(4)
0.0403(3)
0.0157(4)
0.0136(4)
0.0372(4)
0.0627(4)
0.0634(4)
−0.0344(3)
−0.0467(4)
−0.1046(4)
−0.1504(4)
−0.1377(4)
−0.0812(4)
0.0785(3)
0.1337(3)
0.1586(3)
0.1301(3)
0.0767(4)
0.0506(3)
−0.0518(6)
0.6398(10)
0.4819(9)
0.4288(10)
0.5154(11)
0.7512(11)
0.8915(12)
0.9516(11)
0.8681(11)
0.7327(9)
0.6643(10)
0.3937(8)
0.3039(8)
0.0701(8)
0.2461(8)
3. Experimental details
Standard Schlenk techniques were used for all manip-
ulations involving oxygen- or moisture-sensitive com-
pounds. Solvents used were freshly distilled over
appropriate drying agents prior to use. When procedures
involved materials that were not air-sensitive, solvent
removal under reduced pressure was achieved using a
rotary evaporator. Routine recrystallisations were
achieved by the following method; the sample was
dissolved in a low b.p. solvent and a higher b.p. sol-
C(9)
C(10)
C(11)
C(12)
C(13)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
C(71)
C(72)
C(73)
C(74)
C(75)
C(76)
0.3321(11) −0.0487(5)
0.2792(14) −0.1105(6)
0.1431(12) −0.1143(5)
0.0537(10) −0.0586(5)
Table 1
Crystal
data
and
structure
refinement
parameters
for
Os(C11H8)(CO)2(PPh3)2 (4)
0.1065(9)
0.4926(7)
0.5893(9)
0.7300(10)
0.7769(9)
0.6837(10)
0.5423(8)
0.2230(7)
0.1803(9)
0.1227(10)
0.1520(13)
0.1104(10)
0.2073(11)
0.4644(7)
0.5659(8)
0.7044(9)
0.7464(9)
0.6483(10)
0.5072(8)
0.2192(7)
0.0817(8)
0.0247(9)
0.1059(10)
0.2405(10)
0.2985(9)
0.1816(7)
0.1171(8)
0.0343(9)
0.0162(8)
0.0788(9)
0.1615(8)
0.0020(4)
0.0689(4)
0.0766(5)
0.0613(5)
0.0391(5)
0.0316(6)
0.0463(5)
0.0796(4)
0.0148(4)
0.0075(5)
0.1320(6)
0.0665(5)
0.1392(5)
0.3436(4)
0.2996(5)
0.3210(5)
0.3856(5)
0.4291(5)
0.4086(4)
0.3163(3)
0.2948(4)
0.3003(5)
0.3263(4)
0.3480(5)
0.3422(4)
0.3810(4)
0.3698(4)
0.4224(4)
0.4873(4)
0.4990(4)
0.4462(4)
Empirical formula
Formula weight
Temperature
C49H38O2OsP2
910.93
203(2) K
˚
Wavelength
0.71073 A
Crystal system
Space group
Monoclinic
P21/n
Unit cell dimensions
˚
a (A)
9.4845(3)
18.6973(6)
22.3614(8)
91.1550(10)
3964.6(2)
4
1.526
3.337
1816
˚
b (A)
˚
c (A)
i (°)
3
˚
V (A )
Z
Dcalc. (g cm−3
)
Absorption coefficient (mm−1
F(000)
)
Crystal size
0.35×0.20×0.12 mm
Theta range for data collection 1.42–25.00
(°)
Index ranges
−95h511, −225k516,
−265l526
Reflections collected
21570
Reflections observed [I\2|(I)] 5667
Independent reflections
Max/min transmission
Refinement method
Data/restraints/parameters
Final R indices [I\2|(I)]
R indices (all data)
6975 [Rint=0.0587]
0.6 902, 0.3880
Full-matrix least-squares on F2
6975/0/487
R1=0.0463, awR2=0.0929
R1=0.0656, awR2=0.1047
Goodness-of-fit on F2
Largest difference peak and
hole
0.957
−3
˚
0. 642 and −0.957 e A
a Weighting scheme calc. w=1/[|2(F2o)+(0.0000P)2+36.8879P]
where P=(F2o+2Fc2)/3.
U(eq) is defined as one third of the trace of the orthogonalised Uij
tensor.

L.-J. Baker et al. / Journal of Organometallic Chemistry 565 (1998) 153–158
157
Table 3
spectrometer operating at 70 eV using argon as a source
and m-nitrobenzyl alcohol was used as the matrix.
Analytical data were obtained from the Microanalytical
Laboratory, University of Otago. Melting points were
determined on a Reichert microscope hot stage and are
uncorrected.
[Os(ꢁC-1-naphthyl)(CO)2(PPh3)2]ClO4 and [Os(ꢁC-2-
naphthyl)(CO)2(PPh3)2]ClO4 was synthesised by litera-
ture methods [5].
˚
Selected bond lengths (A) and bond angles (°) for
Os(C11H8)(CO)2(PPh3)2 (4)
˚
Bond lengths (A)
Os(1)–C(11)
Os(1)–C(12)
Os(1)–P(2)
C(1)–C(9)
C(2)–C(3)
C(4)–C(10)
C(5)–C(10)
C(7)–C(8)
C(9)–C(10)
1.900(8)
1.916(8)
Os(1)–C(13)
Os(1)–P(1)
1.912(8)
2.3658(18)
1.518(12)
1.356(11)
1.339(12)
1.362(14)
1.351(14)
1.314(13)
2.3680(18) C(1)–C(2)
1.562(12)
1.461(12)
1.429(13)
1.428(12)
1.411(13)
1.413(12)
C(2)–C(11)
C(3)–C(4)
C(5)–C(6)
C(6)–C(7)
C(8)–C(9)
3.1. Os(C11H8)(CO)2(PPh3)2 (3)
Bond angles (°)
C(11)–Os(1)–C(13) 127.8(3)
A sample of [Os(ꢁC-1-naphthyl)(CO)2(PPh3)2]ClO4
(200 mg, 0.200 mmol) was dissolved in THF (30 ml) in
a small Schlenk tube and LiEt3BH (1 M solution in
THF, 0.20 ml, 0.20 mmol) was added causing the red
solution to discolour. Ethanol (30 ml) was added and
the solvent volume decreased on a rotary evaporator.
The product was collected and recrystallised from
dichloromethane–ethanol (1:1) to give pure 3 as pale
yellow crystals, 140 mg (78%), m.p. 175–176°C, M=
910.99 g mol−1, m/z 912.1942. C49H38O2OsP2 requires
912.1962. Anal. Found: C, 62.06; H, 4.08%.
C49H38O2OsP2 ·CH2Cl2 requires C, 62.36; H, 4.12%. IR:
C(11)–Os(1)–C(12) 133.2(3)
C(13)–Os(1)–C(12)
C(11)–C(2)–C(3)
C(3)–C(2)–C(1)
C(3)–C(4)–C(10)
C(7)–C(6)–C(5)
C(9)–C(8)–C(7)
C(8)–C(9)–C(1)
C(9)–C(10)–C(4)
C(4)–C(10)–C(5)
99.0(3)
121.7(8)
117.8(7)
122.1(9)
121.6(9)
119.1(10)
120.4(9)
123.2(8)
120.7(9)
C(2)–C(1)–C(9)
C(11)–C(2)–C(1)
C(4)–C(3)–C(2)
C(6)–C(5)–C(10)
C(6)–C(7)–C(8)
C(8)–C(9)–C(10)
C(10)–C(9)–C(1)
C(9)–C(10)–C(5)
115.2(7)
120.4(8)
121.8(9)
119.9(10)
119.9(10)
123.6(9)
115.9(8)
115.8(9)
1
vent, in which the compound was insoluble, was added.
Evaporation at reduced pressure effected gradual
crystallisation.
1955s, 1982s w(CO); 1615, 1581m cm−1. H-NMR: 2.8
3
(m, 2H, H4); 4.8 (bd, 1H, H3, JHH=9.1); 5.7 (bd, 1H,
3
H2, JHH=9.6); 6.7 (m, 4H, H5, 6, 7, 8); 7.17–7.54 (m,
IR spectra (4000–400 cm−1) were recorded on a Bio
Rad FTS-7 FTIR spectrophotometer. All spectra were
30H, PPh3). 31P-decoupled 1H-NMR: l 2.8 (m, 2H,
H4); 4.8 (d, 1H, H3, 3JHH=9.1); 5.7 (d, 1H, H2,
3JHH=9.6); 6.7 (m, 4H, H5, 6, 7, 8); 7.17–7.54 (m,
1
recorded as Nujol mulls between KBr plates. H-NMR,
13C-NMR, 31P-NMR, COSY and HMQC spectra were
recorded on Bruker DRX-400 or AC-200 instruments.
All NMR experiments were performed at 25°C using
CDCl3 as solvent, referenced to TMS. All 13C-NMR
were recorded in the presence of chromium acetylaceto-
nate as spin relaxant (d1=0.1 s). The numbering sys-
tem used for proton and carbon assignments is given in
Scheme 3. All 31P-NMR were collected at 25°C in
CDCl3 and referenced to phosphoric acid (l=0.00
ppm). FAB+ mass spectra were recorded on a VG 7070
PPh3) ppm. 13C-NMR: l 300.7 (t, C11, JCP=20.1);
2
191.2 (t, CO, 2JCP=7.0); 190.8 (t, CO, 2JCP=9.8);
3
129.2 (t, C1, JCP=9); 127.0 (s, C5/6/7/8); 125.2 (s,
C5/6/7/8); 124.4 (s, C5/6/7/8); 123.9 (s, C5/6/7/8);
5
4
121.0 (t, C3, JCP=6); 116.0 (t, C2, JCP=5); 30.8 (s,
C4); 135.210 (t% {see ref. [10] for explanations of sym-
1,3
bols used and assignments made}, PPh3 ipso,
J
=
CP
54.3); 134.37 (t%, PPh3 meta, 3,5JCP=10.9); 130.23 (s,
PPh3 para); 127.87 (t%, PPh3 ortho, 2,4JCP=9.1) ppm.
31P-NMR: l 12.56 (s, PPh3) ppm.
3.2. Os(C11H8)(CO)2(PPh3)2 (4)
A sample of [Os(ꢁC-2-naphthyl)(CO)2(PPh3)2]ClO4
(200 mg, 0.200 mmol) was treated as in Section 3.1 to
yield bright yellow crystals of 4, 160 mg (89%), m.p.
232°C, M=910.99
g
mol−1
,
m/z 912.1974.
C49H38O2OsP2 requires 912.1962. Anal Found: C,
64.37; H, 4.33%. C49H38O2OsP2 requires C, 64.60; H,
4.20%. IR: 1957s, 1894s w(CO); 1612m, 1587w, 1553w,
1
5
1220w cm−1. H-NMR: l 2.9 (t, 2H, H1, JHP=7.7);
2
6
5.3 (dt, 1H, H4, JHH=9.5, JHP=2.7); 5.7 (dt, 1H,
2
5
2
H3, JHH=8.9, JHP=1.7); 6.5 (dd, 1H, H8, JHH
=
7.0); 6.6 (dd, 1H, H5, 2JHH=6.9); 6.8 (td, 1H, H7,
2JHH=7.0, 2JHH=1.4); 6.9 (td, 1H, H6, 2JHH=7.0,
2JHH=1.4); 7.25–7.54 (m, 30H, PPh3) ppm. 31P-decou-
Scheme 4. Addition of HCl to the vinylidene complexes, 3 or 4,
resulting in the corresponding naphthylmethyl complexes 5 or 6.

158
L.-J. Baker et al. / Journal of Organometallic Chemistry 565 (1998) 153–158
pled 1H-NMR: l 2.9 (s, 2H, H1); 5.3 (d, 1H, H4,
0.0514). Unit cell parameters were obtained by least-
squares fit to all reflections with I\10|(I).
2
2JHH=9.5); 5.7 (d, 1H, H3, JHH=8.9); 6.5 (dd, 1H,
2
2
H8, JHH=7.0); 6.6 (dd, 1H, H5, JHH=6.9); 6.8 (td,
1H, H7, 2JHH=7.0, 3JHH=1.4); 6.9 (td, 1H, H6,
2JHH=7.0, 3JHH=1.4); 7.25–7.54 (m, 30H, PPh3) ppm.
The structure was solved by Patterson and Fourier
techniques and refined by full-matrix least-squares on
F2. Hydrogen atoms were placed geometrically and
refined with a riding model with U(iso) 20%\U(eq) of
the carrier atom. All non-H atoms were allowed to
assume anisotropic motion. Refinement converged to
conventional R=0.0461, wR2=0.0826 for 5666 ob-
served reflections with I\2|(I). Programs: Siemens
SMART and SAINT for data collection and reduction,
SHELXTL [11] for structure solution and refinement.
Crystal data and structure refinement parameters, final
atomic coordinates, and selected bond distances and
angles for Os(C11H8)(CO)2(PPh3)2 (4) are given in Ta-
bles 1–3, respectively.
13C-NMR: l 295.7 (t, C11, JCP =24.9); 191.0 (m,
2
3
CO); 127.2 (s, 8); 126.5 (t, C2, JCP=9); 125.1 (s, C6);
124.8 (s, C7); 124.8 (s, C5); 123.7 (t, C3, 4JCP=7);
5
4
118.1 (t, C4, JCP=4); 25.6 (t, C1, JCP=5); 135.44 (t%,
PPh3 ipso, 1,3JCP=54.3); 134.41 (t%, PPh3 meta,
J
=
3,5
CP
12.1); 129.81 (s, PPh3 para); 127.85 (t%, PPh3 ortho,
2,4JCP=10.1) ppm. 31P-NMR: l 12.67 (s, PPh3) ppm.
3.3. Os(CH2-1-naphthyl)Cl(CO)2(PPh3)2 (5)
A sample of Os(C11H8)(CO)2(PPh3)2 (3) (200 mg,
0.219 mmol) was dissolved in dichloromethane (25 ml)
and ethanol (25 ml) in a 100 ml round bottom flask.
Concentrated HCl (1 ml) was added and the solution
was stirred at 30°C for 2 min. The resulting white
product was collected by filtration and recrystallised
from dichloromethane–ethanol to yield pure 7 as a
cream powder, 150 mg (72%), m.p. 123–125°C, M=
947.45 g mol−1, m/z 948. Anal. Found: C, 60.54; H,
4.30%. C49H39ClO2P2Os·1/2CH2Cl2 requires C, 60.06;
H, 4.07%. IR: l 2017s, 1938s n(CO); 1582w, 1261w
4. Supplementary material available
Supplementary data comprises H atom positions,
anisotropic thermal parameters, and full listings of
bond lengths and angles. Structure factor tables are
available on request from the authors.
1
3
ppm. H-NMR: l 3.3 (t, 2H, CH2, JHP=8.0); 7.0–8.5
Acknowledgements
(m, 7H, naphthyl, 30H, PPh3) ppm. 13C-NMR: l 181.0
(t, CO, JCP=6.6); 178.1 (t, CO, JCP=8.0); 31.8 (s,
CH2) ppm.
2
2
We thank The University of Auckland Research
Committee for partial support of this work through
grants-in-aid.
3.4. Os(CH2-2-naphthyl)Cl(CO)2(PPh3)2 (6)
A sample of Os(C11H8)(CO)2(PPh3)2 (4) (200 mg,
0.219 mmol) was treated as in Section 3.3 above to
yield pure 6 as white crystals, 165 mg (79%), m.p.
209–210°C, M=947.45 g mol−1, m/z 948. Anal.
Found: C, 59.22; H, 3.56%. C49H39ClO2P2Os·2/
3CH2Cl2 requires: C, 59.41; H, 4.05%. IR: 2025s, 1955s
References
[1] (a) H. Fischer, P. Hofmann, F.R. Kreissl, R.R. Schrock, U.
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1
w(CO); 1618w, 1597w, 592w cm−1. H-NMR: l 3.2 (t,
3
2H, CH2, JHP=8.2); 7.0–8.5, (m, 7H, naphthyl, 30H,
PPh3) ppm. 13C-NMR: l 177.2 (t, CO, 2JCP=8.0);
2
176.2 (t, CO, JCP=7.0); 29.7 (s, CH2); 134.02 (t%, PPh3
meta, 3,5JCP=10.1); 132.49 (t%, PPh3 ipso, 1,3JCP=51.3);
2,4
130.26 (s, PPh3 para); 128.25 (t%, PPh3 ortho
J
=
CP
10.1) ppm.
3.5. X-ray crystal structure determination of
Os(C11H8)(CO)2(PPh3)2 (4)
[8] B. Weber, P. Steinert, B Windmuller, J. Wolf, H. Werner, J.
Chem. Soc. Chem. Commun. (1994) 2595–2596.
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Organometallics 15 (1996) 1793–1803.
Data were collected on a Siemens SMART area
detector diffractometer using 0.3° frames and 3D
profile fitting. Lorentz and polarisation corrections and
an empirical absorption correction were applied to the
29113 measured reflections and equivalent reflections
[11] SHELXTL V5.0, Siemens Energy and Automation, Madison,
WI, 53719-1173.
averaged, yielding 6973 unique reflections (Rint
=