Synthesis, structural characterisation and reactivity of molybdenum half-sandwich complexes containing keto- and amido-phosphines

Article abstract of DOI:10.1016/S0022-328X(02)02017-X

The keto-functionalised N-pyrrolyl phosphine ligand PPh₂NC₄H₃{C(O)CH₃-2} L¹ reacts with [MoCl(CO)₃ (η⁵-C₅R₅)] (R = H, Me) to give [MoCl(CO)₂ (CO)

Full text of DOI:10.1016/S0022-328X(02)02017-X

Journal of Organometallic Chemistry 665 (2003) 15ꢁ22
/
www.elsevier.com/locate/jorganchem
Synthesis, structural characterisation and reactivity of molybdenum
half-sandwich complexes containing keto- and amido-phosphines
Christopher D. Andrews a, Andrew D. Burrows a,*, John C. Jeffery b, Jason M. Lynam b,
Mary F. Mahon a
a Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK
b School of Chemistry, University of Bristol, Cantocks Close, Bristol BS8 1TS, UK
Abstract
The keto-functionalised N-pyrrolyl phosphine ligand PPh2NC4H3{C(O)CH3-2} L1 reacts with [MoCl(CO)3(h5-C5R5)] (Rꢀ
Me) to give [MoCl(CO)2(L1-k1P)(h5-C5R5)] (Rꢀ 1a; Me 1b). The phosphine ligands PPh2CH2C(O)Ph (L2) and
PPh2CH2C(O)NPh2 (L3) react with [MoCl(CO)3(h5-C5R5)] in an analogous manner to give the compounds [MoCl(CO)2(L-
k1P)(h5-C5R5)] (LꢀL2, Rꢀ L3, Rꢀ
H 2a, Me 2b; Lꢀ H 3a, Me 3b). Compounds 1ꢁ3 react with AgBF4 to give [Mo(CO)2(L-
k2P,O)(h5-C5R5)]BF4 (LꢀL1, Rꢀ L2, Rꢀ L3, Rꢀ
H 4a, Me 4b; Lꢀ H 5a, Me 5b; Lꢀ H 6a, Me 6b) following displacement of
chloride. The X-ray crystal structure of 4a revealed a lengthening of both MoꢁP and CÄO bonds on co-ordination of the keto
group. The lability of the co-ordinated keto or amido group has been assessed by addition of a range of phosphines to compounds
4ꢁ PMe3 7a; PMe2Ph
6. Compound 4a reacts with PMe3, PMe2Ph and PMePh2 to give [Mo(CO)2(L1-k1P)(L)(h5-C5H5)]BF4 (Lꢀ
7b; PMePh2 7c) but does not react with PPh3, 5a reacts with PMe2Ph, PMePh2 and PPh3 to give [Mo(CO)2(L2-k1P)(L)(h5-
C5H5)]BF4 (Lꢀ
PMe2Ph 8b; PMePh2 8c; PPh3 8d), and 6a reacts with PMe3, PMe2Ph, PMePh2 and PPh3 to give [Mo(CO)2(L3-
k1P)(L)(h5-C5H5)]BF4 (Lꢀ
PMe3 10a; PMe2Ph 10b; PMePh2 10c; PPh3 10d). No reaction was observed for the pentamethylcy-
clopentadienyl compounds 4bꢁ6b with PMe3, PMe2Ph, PMePh2 or PPh3. These results are consistent with the displacement of the
/H,
/
H
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
co-ordinated oxygen atom being influenced by the steric properties of the P,O-ligand, with PPh3 displacing the keto group from L2
but not from the bulkier L1. In the reaction of [Mo(CO)2(L2-k2P,O)(h5-C5H5)]BF4 (5a) with PMe3 the phosphine does not displace
the keto group, instead it acts as a base, with the only observed molybdenum-containing product being the enolate compound
[Mo(CO)2{PPh2CHÄ
C(O)Ph-k2P,O}(h5-C5H5)] 9. Compound 9 can also be formed from the reaction of 2a with BuLi or NEt3, and
a single crystal X-ray analysis has confirmed the enolate structure.
/
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Keto-phosphines; Amido-phosphines; Molybdenum; Half-sandwich compounds
1. Introduction
these ligands with earlier transition metals has received
far less attention. Recently, we reported the synthesis of
the keto-functionalised N-pyrrolyl phosphine ligand
PPh2NC4H3{C(O)CH3-2} (L1) and the reaction of this
Bifunctional ligands containing both hard and soft
donor atoms are of interest catalytically, in part through
their potential for hemilability [1]. Ketophosphines such
as PPh2CH2C(O)Ph have attracted considerable interest
for their ability to act as uni- or bidentate ligands and
for the facile and reversible transformations between the
co-ordination modes [2]. Although the chemistry of
keto- and amido-phosphines with late transition metal
centres has been well developed [3], the reactivity of
ligand
with
[MoCl(CO)3(h5-C5H5)]
to
form
[MoCl(CO)2(L1-k1P)(h5-C5H5)] (1a) [4]. Prior to this,
the only previously reported crystal structure of a group
6 metal ketophosphine complex was of [W(CO)4-
(PPh2OH)(L2)] [L2ꢀ
PPh2CH2C(O)Ph], in which the
/
b-ketophosphine has been formed in situ [5]. Accounts
of molybdenum h6-arene complexes with L2 and amide-
derived ligands PPh2NRC(O)CH3 (RꢀH, Me) have
/
also recently appeared [6], as has a report on molybde-
num(III), -(IV) and -(V) half-sandwich complexes of the
amidophosphine Ph2PCH2C(O)NPh2, L3 [7].
* Corresponding author. Tel.: ꢂ
386-231
E-mail address: a.d.burrows@bath.ac.uk (A.D. Burrows).
/
44-1225-386-529; fax: ꢂ44-1225-
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 2 0 1 7 - X

16
C.D. Andrews et al. / Journal of Organometallic Chemistry 665 (2003) 15ꢁ22
/
In this paper the molybdenum(II) chemistry of 1a and
plexes [Mo(CO)2(L-k2P,O)(h5-C5R5)]BF4 (Lꢀ
H 4a, Me 4b; Lꢀ H 5a, Me 5b; Lꢀ
L2, Rꢀ L3, Rꢀ
6a, Me 6b) in good yield (83ꢁ97%) and these reactions
/
L1, Rꢀ
/
related compounds incorporating L2 and L3 is devel-
oped, and the displacement of the co-ordinated keto or
amido groups on reaction with phosphines investigated.
/
/
/
/H
/
are summarised in Scheme 1. Co-ordination of the
carbonyl group of the phosphines was indicated by the
large decrease in n(CÄ
ordinated ligands (Dn(CÄ
The coupling patterns observed for the metal carbonyl
peaks in the 13C{1H}-NMR spectra for complexes 4ꢁ
were similar to those observed for complexes 1ꢁ3,
/
O) from that of the k1P-co-
O)ꢀ 97 to ꢃ
122 cmꢃ1).
/
/
ꢃ
/
/
2. Results and discussion
/
6
On heating [MoCl(CO)3(h5-C5R5)] (Rꢀ
reflux for 6 h with one equivalent of L1, L2 or L3, the
/
H or Me) at
/
suggesting the retention of the cis-conformation. In
contrast, the reaction of [Mo(m-Cl)2(h5-C5H5)]2 with L3
leads to both the cis and trans isomers of [MoCl2(L3-
k2P,O)(h5-C5H5)] [7].
The identity of 4a was confirmed by X-ray crystal-
lography analysis, and the structure of the cation is
shown in Fig. 1 with selected bond distances and angles
given in Table 1. The complex cation adopts a pseudo-
square pyramidal metal geometry, with the cis carbo-
nyls, oxygen and phosphorus atoms forming the base of
complexes [MoCl(CO)2(L)(h5-C5R5)] (Lꢀ
1a, Me 1b; Lꢀ H 2a, Me 2b; Lꢀ
L2, Rꢀ
3a, Me 3b) were formed in good yield (79ꢁ
/
L1, Rꢀ
/
H
H
/
/
/
L3, Rꢀ
/
/
93%) as dark
red or orange powders. Co-ordination of the phospho-
rus atom was generally accompanied by a significant
downfield shift in d(31P) relative to the free ligands
[Ddꢀ
small [Ddꢀ
donor was reflected in the small changes in n(CÄ
/
/
56.4ꢁ
/
69.5 ppm], though for 1b the shift is very
2.4 ppm]. Non-co-ordination of the oxygen
O)
15 to ꢃ14
/
/
relative to the free ligands [Dn(CÄ
/
O)ꢀ
/
ꢂ
/
the pyramid, and the cyclopentadienyl ring the apex.
˚
O bond length of 1.251(3) A is longer than
cmꢃ1]. The value of Dd(31P) is usually a reliable
indicator of coordination mode, so the chemical shift
observed for 1b is surprising and difficult to rationalise.
The keto CÄ
/
that observed in both the free ligand L1 and in complex
However, the H- and 13C{1H}-NMR spectra, together
1
with the IR spectrum, microanalysis and reactivity all
suggest that the proposed structure is correct.
The crystal structure of complex 1a demonstrated the
cis (or lat) arrangement of ligands around the molyb-
denum centre [4], and spectroscopic evidence revealed
that this orientation was also present in the other
complexes 1ꢁ3. Hence, two metal carbonyl resonances
/
were observed in the 13C{1H}-NMR spectra as doublets,
2
with one having a JCP coupling constant significantly
larger (18.2ꢁ
/
31.4 Hz) than the other (58.2 Hz), while in
/
1
the H-NMR spectra for complexes 2-3, the methylene
protons were seen as a pair of mutually coupled doublet
of doublets, indicating their inequivalence. The reaction
of L3 with [MoCl(CO)3(h5-C5Me5)] to give a P-co-
ordinated complex contrasts with the observation that
[Mo(m-Cl)2(h5-C5Me5)]2 does not react with L3 [7].
Addition of one equivalent of AgBF4 to dichloro-
Fig. 1. Structure of the cation present in [Mo(CO)2(L1-k2P,O)(h5-
C5H5)]BF4 (4a) with thermal ellipsoids shown at the 30% probability
level.
methane solutions of complexes 1ꢁ/3 resulted in the
precipitation of AgCl and the formation of the com-
Scheme 1.

C.D. Andrews et al. / Journal of Organometallic Chemistry 665 (2003) 15ꢁ
/
22
17
Table 1
The lability of the co-ordinated keto- or amido-
groups in complexes 4ꢁ6 was also probed by the
investigation of the reactions between these complexes
and tertiary phosphines. Each of the complexes 4ꢁ6 was
1
˚
Selected bond lengths (A) and bond angles (8) for [Mo(CO)2(L -
k2P,O)(h5-C5H5)]BF4 (4a) and the equivalent parameters for 1a where
relevant [4]
/
/
4a
1a
reacted with the phosphines from the series PMe3,
PMe2Ph, PMePh2 and PPh3 which span a range of
steric and electronic properties, and the reactions are
summarised in Scheme 2.
Bond lengths
Moꢁ
Moꢁ
Moꢁ
Moꢁ
Pꢁ
N(51)ꢁ
N(51)ꢁ
C(52)ꢁ
C(53)ꢁ
C(54)ꢁ
C(55)ꢁ
C(56)ꢁ
C(56)ꢁ
/
C(1)
C(2)
P
1.993(3)
1.978(3)
2.4399(6)
2.1619(17)
1.733(2)
1.383(3)
1.406(3)
1.369(4)
1.395(4)
1.387(4)
1.427(3)
1.251(3)
1.505(3)
1.961(5)
1.969(6)
2.5176(16)
/
/
Complex 4a was observed to react with PMe3,
PMe2Ph and PMePh2 to give the complexes
/O(57)
/
N(51)
1.748(4)
1.383(7)
1.407(6)
1.355(8)
1.395(8)
1.366(8)
1.451(7)
1.222(7)
1.495(7)
[Mo(CO)2(L-k1P)(L1-k1P)(h5-C5H5)]BF4
7a, PMe2Ph 7b, PMePh2 7c] as orange oils. The non-
[LꢀPMe3
/
/C(52)
/C(55)
co-ordination of the keto group was indicated by the
O) band to a frequency similar to that
/
C(53)
C(54)
C(55)
C(56)
O(57)
C(58)
/
return of the n(CÄ
/
observed for the free ligand. The 13C{1H}-NMR spectra
showed one environment for the carbonyl ligands in all
/
/
/
cases, in contrast to complexes 1ꢁ6, which suggested
/
/
that 7 exists in the trans (or diag) conformation. This
resonance was observed as a pseudo-triplet, due to the
Bond angles
Pꢁ
Pꢁ
Pꢁ
C(1)ꢁ
C(1)ꢁ
C(2)ꢁ
/
Moꢁ
Moꢁ
Moꢁ
/
O(57)
C(1)
C(2)
83.61(5)
117.29(9)
78.06(7)
2
similar magnitudes of the two JCP coupling constants.
/
/
111.62(16)
77.86(16)
76.0(2)
1
The trans orientation was also supported by the H-
/
/
/
Moꢁ
Moꢁ
Moꢁ
/
C(2)
O(57)
O(57)
77.55(11)
79.57(10)
139.64(9)
NMR spectrum for 7b, in which the two methyl groups
on the PMe2Ph ligand were observed to be equivalent.
In contrast to these reactions, addition of PPh3 to 4a led
to no reaction, even after 14 days.
/
/
/
/
Complex 5a was observed to react with PMe2Ph,
PMePh2 and PPh3 to give the complexes [Mo(CO)2(L-
˚
1a [1.216(2) and 1.222(6) A, respectively [4]], consistent
k1P)(L2-k1P)(h5-C5H5)]BF4 [Lꢀ
/PMe2Ph 8b, PMePh2
with a reduction in bond order upon co-ordination. The
˚
PꢁN bond length of 1.733(2) A is similar to that
/
8c, PPh3 8d] as red oils. IR and NMR spectroscopic data
are consistent with formation of the trans isomer. The
reaction with PMe3 did not give [Mo(CO)2(PMe3)(L2-
k1P)(h5-C5H5)]BF4, as anticipated, but instead the
˚
observed in 1a within experimental error [1.748(4) A],
1
but shorter than in the free phosphine L [1.7637(14) A].
˚
The sum of angles around the nitrogen atom in 4a is
3608 as in both L1 and 1a. The bite angle in 4a is
83.61(5)8, which is close to that observed for the
neutral
complex
[Mo(CO)2{PPh2CHÄ
/
C(O)Ph-
k2P,O}(h5-C5H5)] 9. The identity of 9 was confirmed
spectroscopically and by a single crystal analysis, as
detailed later. The amidophosphine complex 6a reacted
with PMe3, PMe2Ph, PMePh2 and PPh3 to give the
phosphineꢁphosphine oxide ligand PEt2CH2CH2-
/
P(O)Et2 which also forms a six-membered chelate ring
around molybdenum [83.0(2)8] [8].
Complexes 4a and 5a were also prepared by addition
complexes
[LꢀPMe3 10a, Lꢀ
[Mo(CO)2(L-k1P)(L3-k1P)(h5-C5H5)]BF4
PMe2Ph 10b, PMePh2 10c, PPh3
of HBF4×
[Mo(CH3)(CO)3(h5-C5H5)]. Reaction of complexes 4ꢁ
with NEt3BzCl led to re-formation of complexes 1ꢁ3,
/
OEt2 and the appropriate phosphine to
/
/
/
6
10d] as red or orange oils, again with trans orientation
of the phosphines. However, the reactions were all
significantly slower than those observed for the L2
/
hence the chloride anion is able to displace the co-
ordinated keto or amido group.
complexes, with the reactions to form 10a
/
c taking 7
ꢁ
Scheme 2.

18
C.D. Andrews et al. / Journal of Organometallic Chemistry 665 (2003) 15ꢁ22
/
days to reach completion, compared with 18 h for 8bꢁ
/
c.
phosphine ligands in the products from these reactions
also serves to reduce the steric interactions between the
bulky ligands. The Cambridge Structural Database [10]
reveals that of the six structures known for the cations
[M(CO)2P1P2(h5-C5R5)]ꢂ, where M is a Group 6 metal,
Both the reactions of 4a and 5a with PPh3 were
considerably slower than those with the other tertiary
phosphines, taking 7 and 14 days to reach completion,
to give complexes 8d and 10d, respectively.
In contrast to these observations on the reactivity of
the cyclopentadienyl complexes 4a, 5a and 6a, no
reaction was observed on addition of any of the same
range of tertiary phosphines to the pentamethylcyclo-
pentadienyl complexes 4b, 5b and 6b. After 14 days the
only species observed in the 31P{1H}- and 1H-NMR
spectra were starting materials.
P1 and P2 are phosphines or phosphites, and Rꢀ
H or
/
Me, five exist as the trans isomer. The only example of
the cis orientation is for [Cr(CO)2{P(OMe)3}2(h5-
C5Me5)]BF4 [11] where both cis and trans structural
isomers were formed together.
In contrast to the addition reactions observed with
other tertiary phosphines, complex 5a is deprotonated
The reaction of [Mo(CO)2(L-k2P,O)(h5-C5R5)]ꢂ
with a 2-electron donor L? to give [Mo(CO)2(L-
k1P)(L?)(h5-C5R5)]ꢂ is likely to occur via a 16-electron
intermediate [Mo(CO)2(L-k1P)(h5-C5R5)]ꢂ, present in
solution as a minor component in equilibrium with
[Mo(CO)2(L-k2P,O)(h5-C5R5)]ꢂ. Although there is no
direct evidence for this intermediate, 31P magnetisation
transfer experiments suggest that the phosphite ex-
by PMe3 to give [Mo(CO)2{PPh2CHÄ
/
C(O)Ph-
k2P,O}(h5-C5H5)] (9). Formation of the enolate group
is indicated by the low value for the carbonyl stretching
frequency [n(C
/
Á Á Á
/
Cꢂ
/
C
/
Á Á Á
/
O)ꢀ
/
1460 cmꢃ1, Dnꢀ
/
ꢃ98
/
¯
¯
cmꢃ1 relative to 5a]. The two inequivalent methylene
protons observed for 5a were no longer present in the
1H-NMR spectrum, instead only a doublet (2JHP
Hz) integrating to one proton was observed.
ꢀ1.2
/
change
reaction
of
[Mo{P(OMe)3}2{h2(4e)-
The structure of 9 was confirmed by a single crystal
X-ray structural analysis. The molecular structure is
shown in Fig. 2, with selected bond lengths and angles
given in Table 2. The complex adopts a pseudo-square
pyramidal metal geometry, with the cis carbonyls,
oxygen and phosphorus atoms forming the base of the
pyramid, and the cyclopentadienyl ring the apex. The
single proton on the carbon atom C(9) was readily
PhC2Ph}(h5-C5H5)]ꢂ occurs via a 16-electron inter-
mediate formed by a change in the bonding mode of
the alkyne from h2(4e) to h2(2e) [9].
The observation of no reaction with the pentamethyl-
cyclopentadienyl complexes 4b, 5b and 6b suggests the
reaction of this intermediate with L? is sterically
controlled, with the bulky pentamethylcyclopentadienyl
group preventing attack when L? is a phosphine, but
allowing it when L? is the smaller chloride. This is also
supported by the longer reaction times required by PPh3
in comparison with the other phosphines used, and by
the faster reactions observed for the b-ketophosphine
complex 5a in comparison with the N-pyrrolyl ketopho-
sphine complex 4a and the b-amidophosphine complex
6a, which is consistent with the smaller size of L2 versus
L1 and L3. The observed trans orientation of the
located during the refinement. Both the Cꢁ
/
O and CÄ
/C
˚
bond distances [1.319(5) and 1.372(5) A, respectively]
support the description of 9 as an enolate, and are
similar to those parameters observed in other com-
pounds containing [PPh2CHÄ
/
C(O)Ph]ꢃ [3]. Formation
of enolate compounds from the reaction of co-ordinated
L2 with base are well-established in later transition metal
chemistry, and the molybdenum(II) dimer [Mo(h3-
C3H5)(h6-C6H6)(m-Cl)]2 reacts with L2 in ethanol to
Fig. 2. Molecular structure of [Mo(CO)2{PPh2CHÄ
C(O)Ph-k2P,O}(h5-C5H5)] (9) with thermal ellipsoids shown at the 30% probability level.
/

C.D. Andrews et al. / Journal of Organometallic Chemistry 665 (2003) 15ꢁ
/
22
19
Table 2
brought to reflux for 6 h resulting in the formation of a
red precipitate. This was separated by filtration, the
volatiles were removed in vacuo and the residue
˚
Selected bond lengths (A) and bond angles (8) for
[Mo(CO)2{PPh2CHÄC(O)Ph-k2P,O}(h5-C5H5)] (9)
recrystallised from dichloromethaneꢁ/toluene to give
Bond lengths
the product as a dark red powder.
1a: Yield 89%. Anal. Found (Calc. for C25H21ClMo-
Mo(1)ꢁ
Mo(1)ꢁ
Mo(1)ꢁ
Mo(1)ꢁ
P(1)ꢁ
C(8)ꢁ
C(8)ꢁ
/
P(1)
O(3)
C(1)
C(2)
2.4475(10)
2.151(2)
1.977(4)
1.974(4)
1.765(4)
1.372(5)
1.319(5)
/
NO3P): C 54.9 (55.0), H 3.94 (3.88), N 2.64 (2.57)%. 1H-
/
/
NMR (CDCl3): d 7.72ꢁ7.38 [m, 10H, Ph], 7.20 [m, 1H,
/
/
C(9)
pyr], 6.46 [m, 1H, pyr], 6.21 [m, 1H, pyr], 5.61 [s, 5H,
C5H5], 2.31 [s, 3H, Me]. 13C{1H} (CDCl3): d 254.2 [d,
/
C(9)
/
O(3)
2
2
Bond angles
P(1)ꢁMo(1)ꢁ
P(1)ꢁMo(1)ꢁ
P(1)ꢁMo(1)ꢁ
C(1)ꢁMo(1)ꢁ
C(1)ꢁMo(1)ꢁ
C(2)ꢁMo(1)ꢁ
M-CO, JPC
185.5 [CÄO], 135.2ꢁ
[Me]. 31P{1H} (CDCl3): d 112.2. nmax (CH2Cl2): n(CO)
1970, 1888; n(CÄ
O) 1654 cmꢃ1
1b: Yield 79%. Anal. Found (Calc. for
C30H31ClMoNO3P×1/4CH2Cl2): C 57.5 (57.0), H 4.92
(4.98), N 2.39 (2.20)%. H-NMR (CDCl3): d 7.39ꢁ
ꢀ
/
31.4 Hz], 242.9 [d, Mꢁ
/
CO, JPC
B1 Hz],
/
/
/
O(3)
C(1)
C(2)
76.54(7)
114.62(12)
78.77(12)
75.43(17)
84.22(13)
137.53(17)
/
/
128.0 [m, Ph/pyr], 96.1 [C5H5], 26.0
/
/
/
/
/
.
/
/
C(2)
O(3)
O(3)
/
/
/
/
/
1
/7.22
[m, 10H, Ph], 7.12 [m, 1H, pyr], 6.39 [m, 1H, pyr], 6.22
[m, 1H, pyr], 2.41 [s, 3H, Me], 1.94 [s, 15H, C5Me5].
give enolate complexes [6a]. In addition to formation
from the reaction of 5a with PMe3, compound 9 can also
be formed using a more traditional base such as BuLi or
NEt3. The deprotonation reaction is reversible, and
2
13C{1H} (CDCl3): d 246.3 [d, Mꢁ
/CO, JPC
ꢀ/30.5 Hz],
2
CO, JPC
227.4 [d, Mꢁ
/
B
/
5 Hz], 188.1 [CÄ
/
O], 132.8ꢁ
/
124.8 [m, Ph/pyr], 108.8 [C5Me5], 25.7 [Me], 10.7
[C5Me5]. 31P{1H} (CDCl3): d 58.6. nmax (CH2Cl2):
reaction of 9 with HBF4×
of 5a. Neither 4a nor 6a react with base to give
analogous compounds to 9 * in these cases multiple
/OEt2 leads to the re-formation
n(CO) 1964, 1880; n(CÄ
/
O) 1658 cmꢃ1
.
2a: Yield 91%. Anal. Found (Calc. for
/
1
C27H22ClMoO3P): C 57.8 (58.2), H 3.98 (3.98)%. H-
intractable products resulted from the reactions.
NMR (CDCl3): d 7.78ꢁ7.28 [m, 10H, Ph], 5.37 [s, 5H,
/
2
C5H5], 4.41 [dd, 1H, CH2, JHH
2
ꢀ
/
15.6, JHP
ꢀ
/
9.9 Hz],
7.9 Hz]. 13C{1H}
29.5 Hz], 243.6 [d,
4.14 [dd, 1H, CH2, 2JHH
ꢀ
/
15.6, 2JHP
ꢀ
/
3. Experimental
2
CO, JPC
(CDCl3): d 256.8 [d, Mꢁ
/
ꢀ
/
2
1
All experiments were performed in an atmosphere of
dry, oxygen-free nitrogen using standard Schlenk line
techniques. Solvents were dried by conventional meth-
ods and distilled under nitrogen prior to use. The
Mꢁ
137.1ꢁ
20.4 Hz]. 31P{1H} (CDCl3): d 48.2. nmax (CH2Cl2):
n(CO) 1970, 1888; n(CÄ
O) 1656 cmꢃ1
/
CO, JPC
ꢀ
/
8.2 Hz], 195.2 [d, CÄ
/
O, JPC
ꢀ5.7 Hz],
/
1
/
128.2 [m, Ph], 95.2 [C5H5], 36.4 [d, CH2, JPC
ꢀ
/
/
.
complexes
[MoCl(CO)3(h5-C5H5)]
[12]
and
1
2b: Yield 85%. H-NMR (CDCl3): d 7.67ꢁ
/
7.18 [m,
[MoCl(CO)3(h5-C5Me5)] [13], and the ligands
PPh2NC4H3{C(O)Me-2} [4], PPh2CH2C(O)Ph [3a] and
PPh2CH2C(O)NPh2 [14] were prepared by literature
methods. Infrared spectra were recorded on a Nicolet
Nexus FT-IR spectrometer using NaCl solvent cells.
NMR spectra were recorded using JEOL JNM-EX 270
(270 MHz) or Varian Mercury (400 MHz) spectro-
meters, and were referenced internally to the solvent
(13C and 1H), or externally to 85% H3PO4 (31P).
Microanalyses were performed by the University of
Bath service. A number of the compounds could only be
isolated as oils, for which satisfactory microanalyses
could not be obtained. 13C and 31P resonances were
observed as singlets unless otherwise stated.
2
15H, Ph], 4.64 [dd, 1H, CH2, JHH
2
14.9, JHP
2
14.9, JHP
ꢀ
/
ꢀ/8.1
2
Hz], 3.73 [dd, 1H, CH2, JHH
ꢀ
/
ꢀ
/
7.0 Hz],
1.70 [s, 15H, C5Me5]. 13C{1H} (CDCl3): d 259.0 [d, Mꢁ
/
2
2
CO, JPC
195.2 [d, CÄ
106.3 [C5Me5], 34.1 [d, CH2, JPC
ꢀ
/
27.1 Hz], 246.2 [d, Mꢁ
/
CO, JPC
ꢀ
/
5.4 Hz],
127.6 [m, Ph],
2
/
O, JPC
ꢀ
/
8.1 Hz], 137.0ꢁ
/
1
ꢀ
/
13.6 Hz], 10.0
[C5Me5]. 31P{1H} (CDCl3): d 45.4. nmax (CH2Cl2):
n(CO) 1960, 1879; n(CÄ
3a: Yield 93%. Anal. Found (Calc. for
C33H27ClMoNO3P×1/3CH2Cl2): C 59.1 (59.2) H 4.07
(4.12), N 2.02 (2.07)%. H-NMR (CDCl3): d 7.74ꢁ
[m, 15H, Ph], 5.37 [s, 5H, C5H5], 3.51 [dd, 1H, CH2,
/
O) 1656 cmꢃ1
.
/
1
/7.18
2JHH
2JHH
[d, Mꢁ
Hz], 167.3 [CÄ
[d, CH2, 1JPC
(CH2Cl2): n(CO) 1964, 1872; n(CÄ
3b: Yield 79%. Anal. Found (Calc. for
C38H37ClMoNO3P×1/4CH2Cl2): C 62.2 (62.1) H 5.23
(5.11), N 1.90 (1.89)%. H-NMR (CDCl3): d 7.73ꢁ
ꢀ
/
16.0, JHP
ꢀ
/
11.7 Hz], 3.33 [dd, 1H, CH2,
6.9 Hz]. 13C{1H} (CDCl3): d 257.5
19.5 Hz], 243.7 [d, Mꢁ 6.7
CO, 2JPC
O], 142.4ꢁ126.5 [m, Ph], 95.6 [C5H5], 35.7
25.7 Hz]. 31P{1H} (CDCl3): d 52.1. nmax
O) 1666 cmꢃ1
2
2
ꢀ
/
16.0, JHP
CO, 2JPC
ꢀ
/
/
ꢀ
/
/
ꢀ
/
3.1. Preparation of [MoCl(CO)2(L-k1P)(h5-C5R5)]
/
/
(Lꢀ
/
L1, Rꢀ
/
H 1a, Me 1b; Lꢀ
/
L2, Rꢀ
/
H 2a, Me 2b;
ꢀ
/
Lꢀ
/
L3, Rꢀ
/
H 3a, Me 3b)
/
.
[MoCl(CO)3(h5-C5R5)] (200 mg) and one equivalent
of L were dissolved in hexane (20 ml). The solution was
/
1
/7.09

20
C.D. Andrews et al. / Journal of Organometallic Chemistry 665 (2003) 15ꢁ22
/
[m, 15H, Ph], 3.84 [dd, 1H, CH2, 2JHH
ꢀ
/
16.0, 2JHP
ꢀ
/
8.0
6a: Yield 88%. Anal. Found (Calc. for
C33H26BF4MoNO3P×CH2Cl2): C 51.7 (52.1), H 3.98
(3.60), N 1.74 (1.79)%. H-NMR (CDCl3): d 7.61ꢁ
[m, 20H, Ph], 5.51 [s, 5H, C5H5], 4.42 [dd, 1H, CH2,
2
Hz], 3.29 [dd, 1H, CH2, JHH
2
16.0, JHP
ꢀ
/
ꢀ
/
6.5 Hz],
/
1.77 [s, 15H, C5Me5]. 13C{1H} (CDCl3): d 258.6 [d, Mꢁ
/
/7.10
1
2
CO, JPC
2
CO, JPC
ꢀ
/
18.2 Hz], 245.8 [d, Mꢁ
/
ꢀ/4.8 Hz],
167.4 [CÄ
/
O], 121.3ꢁ
/
110.6 [m, Ph], 96.9 [C5Me5] 31.9 [d,
26.0 Hz], 9.8 [Me]. 31P{1H}-NMR
(CDCl3): d 52.1. nmax (CH2Cl2): n(CO) 1944, 1860;
n(CÄ
O) 1669 cmꢃ1
2JHH
ꢀ
/
16.0, 2JHP
ꢀ
/
8.6 Hz], 3.04 [dd, 1H, CH2, 2JHH
ꢀ
/
1
CH2, JPC
ꢀ
/
16.0, 2JHP
ꢀ
/
12.5 Hz]. 13C{1H} (CDCl3): d 250.2 [d, Mꢁ
/
2
2
CO, JCP
ꢀ
/
19.8 Hz], 242.4 [d, Mꢁ
O, 2JCP
8.8 Hz], 141.8ꢁ
[C5H5], 31.7 [d, CH2, 2JCP 16.2 Hz]. 31P{1H} (CDCl3):
d 65.7. nmax (CH2Cl2): n(CO) 1980, 1902; n(CÄO) 1542
cmꢃ1
/
CO, JCP
B
/
2 Hz],
125.4 [m, Ph], 95.8
/
.
179.6 [d, CÄ
/
ꢀ
/
/
ꢀ
/
3.2. Preparation of [Mo(CO)2(L-k2P,O)(h5-C5R5)]
(Lꢀ H 4a, Me 4b; Lꢀ H 5a, Me 5b;
L1, Rꢀ L2, Rꢀ
Lꢀ H 6a, Me 6b)
L3, Rꢀ
/
/
/
/
/
.
1
/
/
6b: Yield 93%. H-NMR (CDCl3): d 7.59ꢁ
/
7.23 [m,
8.6
12.3 Hz],
2
20H, Ph], 4.23 [dd, 1H, CH2, JHH
2
15.1, JHP
2
15.1, JHP
ꢀ
/
ꢀ
/
2
Hz], 2.94 [dd, 1H, CH2, JHH
One equivalent of AgBF4 was added to a solution of
[MoCl(CO)2(L-P)(h5-C5R5)] in dichloromethane (20
mL). The mixture was stirred with the exclusion of light
ꢀ
/
ꢀ
/
1.60 [s, 15H, C5Me5]. 13C{1H} (CDCl3): d 251.1 [d, Mꢁ
/
2
2
CO, JPC
CO, JPC
178.8 [d, CÄ
98.2 [C5Me5], 31.5 [d, CH2, JPC
ꢀ
/
18.6 Hz], 244.3 [d, Mꢁ
O, JPC
/
B
/
2Hz],
109.9 [m, Ph],
15.9 Hz], 10.5
2
for 30 minꢁ
/
2 h, resulting in the formation of AgCl. The
/
ꢀ
/
10.6 Hz], 120.4ꢁ
/
1
solution was filtered through Celite, the solvent removed
in vacuo and the residue recrystallised from
ꢀ
/
[C5Me5]. 31P{1H} (CDCl3): d 57.1. nmax (CH2Cl2):
dichloromethaneꢁ
4a: Yield 97%. Anal. Found (Calc. for
C25H21BF4MoNO3P×1/4CH2Cl2): C 49.2 (49.0), H 3.73
(3.50), N 2.17 (2.26)%. H-NMR (CDCl3): d 7.67ꢁ
/toluene to give a dark red powder.
n(CO) 1963, 1888; n(CÄ
/
O) 1547 cmꢃ1
.
/
3.3. Preparation of [Mo(CO)2(L)(L1-k1P)(h5-
1
/
7.45
C5H5)][BF4] (LꢀPMe3 7a, PMe2Ph 7b, PMePh2 7c)
/
[m, 11H, Ph/pyr], 7.29 [m, 1H, pyr], 6.56 [m, 1H, pyr],
5.55 [s, 5H, C5H5], 2.59 [s, 3H, Me]. 13C{1H} (CDCl3): d
Typical preparation (7c): PMePh2 (21 ml, 0.110 mmol)
was added to a solution of 4a (61 mg, 0.102 mmol) in
CH2Cl2 (15ml) and the solution stirred at room tem-
perature (r.t.) for 48 h. The product was isolated as an
orange oil by addition of hexane to a dichloromethane
2
CO, JPC
248.0 [d, Mꢁ
/
ꢀ
/
30.0 Hz], 240.0 [d, Mꢁ
/
CO,
2JPC
129.7 [m, Ph/pyr], 116.3, [pyr], 97.7 [C5H5], 27.8 [Me].
ꢀ
/
3.2 Hz], 199.3 [d, CÄ
/
ꢀ
/
6.8 Hz], 135.9ꢁ
/
3
O, JPC
31P{1H} (CDCl3): d 114.6. nmax (CH2Cl2): n(CO) 1997,
1928; n(CÄ
/
O) 1553 cmꢃ1
.
solution.
1
1
4b: Yield 83%. H-NMR (CDCl3): d 7.85ꢁ
/7.56 [m,
7a: Yield 85%. H-NMR (CDCl3): d 7.65ꢁ7.20 [m,
20H, Ph], 7.30 [m, 1H, pyr], 7.04 [m, 1H, pyr], 6.44 [m,
/
10H, Ph], 7.20 [m, 1H, pyr], 7.16 [m, 1H, pyr] 6.59 [m,
1H, pyr], 2.79 [s, 3H, Me], 1.66 [s, 15H, C5Me5].
1H, pyr], 5.22 [s, 5H, C5H5], 2.16 [s, 3H, Me], 1.66 [d,
ꢀ
10.3 Hz]. 13C{1H} (CDCl3): 231.1 [t,
2
2
9H, PMe3, JHP
13C{1H} (CDCl3): d 244.4 [d, Mꢁ
/
CO, JPC
ꢀ
/
28.0 Hz],
/
2
2
2
CO, JCP
225.9 [d, Mꢁ
8.1 Hz], 135.1ꢁ
[Me], 10.6 [C5Me5]. 31P{1H} (CDCl3): d 108.9. nmax
(CH2Cl2): n(CO) 1990, 1916; n(CÄ
O) 1558 cmꢃ1
5a: Yield 83%. H-NMR (CDCl3): d 7.98ꢁ7.33 [m,
15H, Ph], 5.53 [s, 5H, C5H5] 5.00 [dd, 1H, CH2, 2JHH
/
CO, JPC
B
/
2 Hz], 202.7 [d, CÄ
/O, JPC
ꢀ
/
Mꢁ
/
ꢀ
/
29.6 Hz], 184.4 [CÄ
/
O], 135.7ꢁ
7.6 Hz], 93.5
35.2 Hz].
/
127.3 [m,
/
123.8 [m, Ph/pyr], 109.4 [C5Me5], 27.3
Ph/pyr], 124.8 [pyr], 111.0 [d, pyr, JCP
ꢀ
/
1
[C5H5], 25.5 [Me], 18.1 [d, PMe3, JCP
ꢀ
/
/
.
31P{1H} (CDCl3): d 125.1 [d, PPh2NC4H3C(O)Me,
1
2
24 Hz], 20.3 [d, PMe3, JPP
/
2JPP
ꢀ
/
ꢀ24 Hz]. nmax
/
ꢀ
/
(CH2Cl2): n(CO) 1972, 1896; n(CÄ
7b: Yield 86%. H-NMR (CDCl3): d 7.68ꢁ7.28 [m,
/
O) 1664 cmꢃ1
.
2
2
1
18.3, JHP
2JHP 12.3 Hz]. 13C{1H} (CDCl3): d 247.0 [d, Mꢁ
2JPC CO, 2JPC
29.7 Hz], 241.9 [d, Mꢁ 2 Hz], 216.1 [d,
CÄO, JPC 10.4 Hz], 137.2ꢁ128.9 [m, Ph], 96.1 [d,
C5H5, JPC 8.3 Hz], 44.7 [d, CH2, JPC
ꢀ
/
9.0 Hz], 3.73 [dd, 1H, CH2, JHH
ꢀ/18.3,
/
ꢀ
/
/
CO,
25H, Ph], 7.15 [m, 1H, pyr], 6.96 [m, 1H, pyr], 6.42 [m,
1H, pyr], 5.14 [s, 5H, C5H5], 2.16 [s, 3H, Me], 1.96 [d,
ꢀ
/
/
B
/
2
/
ꢀ
ꢀ
/
/
6H, PMe2Ph, 2JHP
ꢀ
9.9 Hz]. 13C{1H} (CDCl3): d 231.2
/
2
1
2
[t, JCP
pyr], 112.3 [d, pyr, JCP
/
ꢀ
/28.3 Hz].
ꢀ
/
29.2 Hz], 184.7 [CÄ
/
O], 136.5ꢁ125.9 [m, Ph/
/
31P{1H} (CDCl3): d 72.5. nmax (CH2Cl2): n(CO) 1987,
ꢀ9.6 Hz], 96.3 [C5H5], 25.8 [Me],
/
1
18.8 [d, Me, JCP
1912; n(CÄ
/
O) 1556 cmꢃ1
.
ꢀ
/
34.3 Hz]. 31P{1H} (CDCl3): d 127.7
1
2
[d, PPh2NC4H3C(O)Me, JPP
5b: Yield 95%. H-NMR (CDCl3): d 8.15ꢁ
/7.41 [m,
ꢀ21 Hz], 26.2 [d,
/
2
15H, Ph], 5.00 [dd, 1H, CH2, JHH
2
19.0, JHP
2
PMe2Ph, JPP
ꢀ
/
ꢀ
/
8.2
11.2 Hz],
ꢀ21 Hz]. nmax (CH2Cl2): n(CO) 1974,
/
2
Hz], 4.29 [dd, 1H, CH2, JHH
2
19.0, JHP
ꢀ
/
ꢀ
/
1898; n(CÄ
/
O) 1669 cmꢃ1
.
1.70 [s, 15H, C5Me5]. 13C{1H} (CDCl3): d 251.3 [d, Mꢁ
/
7c: Yield 90%. H-NMR (CDCl3): d 7.75ꢁ
/7.22 [m,
1
2
2
CO, JPC
214.8 [d, CÄ
108.9 [C5Me5], 44.5 [d, CH2, JPC
ꢀ
/
27.2 Hz], 245.8 [d, Mꢁ
/
CO, JPC
12.5 Hz], 133.6ꢁ
B
/
2 Hz],
128.0 [m, Ph],
20H, Ph], 6.60 [m, 1H, pyr], 5.21 [s, 5H, C5H5], 2.21 [d,
9.4 Hz], 2.05 [s, 3H, CH3]. 13C{1H}
2
2
3H, PCH3, JHP
/O, JPC
ꢀ
/
/
ꢀ
/
1
2
(CDCl3): d 230.8 [t, JCP
ꢀ
/
26.5 Hz], 10.2
ꢀ
/
29.2 Hz] 185.1 [CÄ
128.2 [m, Ph/pyr], 126.6
9.5 Hz], 96.1 [C5H5], 25.7
/
O], 137.9
[C5Me5]. 31P{1H} (CDCl3); d 65.6. nmax (CH2Cl2):
[d, pyr, JCP
[pyr], 112.6 [d, pyr, JCP
ꢀ
/
12.4 Hz], 133.9ꢁ
/
n(CO) 1980, 1905; n(CÄ
/
O) 1559 cmꢃ1
.
ꢀ
/

C.D. Andrews et al. / Journal of Organometallic Chemistry 665 (2003) 15ꢁ
/
22
21
1
[Me], 19.8 [d, Me, JCP
ꢀ
/
34.8 Hz]. 31P{1H} (CDCl3): d
(CH2Cl2): n(CO) 1990, 1913; n(C
/
Á Á Á
/
Cꢂ
/
C
/
Á Á Á
/
O) 1460
2
122.5 [d, Ph2PNC4H3C(O)Me, JPP
¯
¯
ꢀ
/
21 Hz], 40.6 [d,
cmꢃ1. Compound 9 was also prepared from the reaction
of 2a with n-butyl lithium and of 5a with PMe3.
2
PPh2Me, JPP
ꢀ21 Hz]. nmax (CH2Cl2): n(CO) 1978,
/
1900; n(CÄ
/
O) 1669 cmꢃ1
.
3.6. Preparation of [Mo(CO)2(L)(L3-k1P)(h5-
3.4. Preparation of [Mo(CO)2(L)(L2-k1P)(h5-
C5H5)][BF4] (LꢀPMe2Ph 8b, PMePh2 8c, PPh3 8d)
C5H5)][BF4] (Lꢀ
/
PMe3 10a, PMe2Ph 10b, PMePh2
/
10c, PPh3 10d)
Typical preparation (8c): PMePh2 (23 ml, 0.114 mmol)
was added to a solution of 5a (68 mg, 0.112 mmol) in
dichloromethane (15 ml) and the solution stirred at r.t.
for 18 h. The product was isolated as an red oil by
Typical preparation (10c): PMePh2 (12 ml, 0.063
mmol) was added to a solution of 6a (44 mg, 0.063
mmol) in CH2Cl2 (15 ml) and the solution stirred at r.t.
for 7 days. The product was isolated as a red oil by
addition of hexane to a dichloromethane solution.
10a: Orange oil, yield 88%. 1H-NMR (CDCl3): d
7.88-6.97 [m, 10H, Ph], 5.36 [s, 5H, C5H5], 3.85 [d, 2H,
addition of hexane to a dichloromethane solution.
1
8b: Yield 88%. H-NMR (CDCl3): d 7.79ꢁ
25H, Ph], 5.28 [s, 5H, C5H5] 4.33 [d, 2H, CH2, JHP
/
7.35 [m,
2
ꢀ
/
2
2
2
8.6 Hz], 2.06 [d, 6H, Me, JHP
ꢀ
/
9.0 Hz]. 13C{1H}
27.6 Hz], 193.0 [d,
128.0 [m, Ph], 94.7 [C5H5],
CH2, JHP
13C{1H} (CDCl3): d 235.7 [t, Mꢁ
ꢀ
/
8.2 Hz], 1.70 [d, 9H, Me, JHP
2
CO, JCP
ꢀ
/
10.2 Hz].
17.6 Hz],
2
(CDCl3): d 234.3 [t, Mꢁ
/
CO, JCP
ꢀ
/
/
ꢀ
/
1
O, JCP
CÄ
/
ꢀ
/
3.7 Hz], 144.8ꢁ
/
165.1 [CÄ
/
O], 134.0ꢁ127.1 [m, Ph], 94.8 [C5H5], 27.4 [d,
/
1
40.7 [d, CH2, JCP
1
1
CH2, JCP
1
16.9 Hz], 18.2 [d, PMe3, JCP
ꢀ
/
28.5 Hz], 18.8 [d, PMe2Ph, JCP
34.2 Hz]. 31P{1H} (CDCl3): d 52.1 [d, PPh2CH2C(O)Ph,
21 Hz], 25.6 [d, PMe2Ph, JPP
(CH2Cl2): n(CO) 1972, 1890; n(CÄ
8c: Yield 90%. H-NMR (CDCl3): d 7.73ꢁ7.27 [m,
ꢀ
/
ꢀ
/
ꢀ34.9 Hz].
/
31P{1H} (CDCl3): d 55.6 [d, PPh2CH2C(O)NPh2,
2JPP
ꢀ
/
ꢀ
/
21 Hz]. nmax
.
2JPP
ꢀ/21 Hz], 22.5 [d, PMe3, JPP
ꢀ21 Hz]. nmax
/
2
2
/
O) 1663 cmꢃ1
(CH2Cl2): n(CO) 1968, 1888; n(CÄ
/
O) 1663 cmꢃ1
.
1
/
10b: Orange oil, yield 85%. 1H-NMR (CDCl3): d
2
30H, Ph], 5.21 [s, 5H, C5H5] 4.42 [d, 2H, CH2, JHP
ꢀ
/
7.61ꢁ
/
6.86 [m, 25H, Ph], 5.07 [s, 5H, C5H5], 3.67 [d, 2H,
2
8.2 Hz], 2.04 [d, 6H, Me, JHP
2
2
CH2, JHP
8.6 Hz], 2.23 [d, 3H, Me, JHP
ꢀ
/
9.0 Hz]. 13C{1H}
27.1 Hz], 193.3 [d,
128.3 [m, Ph], 95.1 [C5H5],
ꢀ
/
ꢀ
/9.9 Hz].
2
2
CO, JCP
(CDCl3): d 234.1 [t, Mꢁ
/
CO, JCP
ꢀ
/
13C{1H} (CDCl3): d 235.3 [t, Mꢁ
/
ꢀ
/
17.6 Hz],
1
O, JCP
CÄ
/
ꢀ
/
4.7 Hz], 134.3ꢁ
/
164.9 [CÄ
/
O], 134.6ꢁ126.5 [m, Ph], 94.7 [C5H5], 27.5 [d,
/
1
40.6 [d, CH2, JCP
1
ꢀ
/
27.1 Hz], 19.9 [d, PPh2Me, JCP
35.6 Hz]. 31P{1H} (CDCl3): d 48.8 [d, PPh2CH2C(O)Ph,
ꢀ
/
CH2, 1JCP
ꢀ
/
17.1 Hz], 18.7 [d, PMe2Ph, 1JCP
ꢀ33.9 Hz].
/
31P{1H} (CDCl3): d 55.8 [d, PPh2CH2C(O)NPh2,
2JPP
ꢀ
/
20 Hz], 41.2 [d, PMePh2, JPP
ꢀ/20 Hz]. nmax
2JPP
ꢀ/21 Hz], 26.5 [d, PMe2Ph, JPP
ꢀ21 Hz]. nmax
/
2
2
(CH2Cl2): n(CO) 1973, 1892; n(CÄ
8d: Reaction time 7 days, yield 94%. 1H-NMR
(CDCl3): d 7.81ꢁ7.33 [m, 30H, Ph], 5.17 [s, 5H, C5H5]
/
O) 1665 cmꢃ1
.
(CH2Cl2): n(CO) 1968, 1888; n(CÄ
/
O) 1663 cmꢃ1
.
1
10c: Yield 86%. H-NMR (CDCl3) d 7.73ꢁ6.86 [m,
/
2
30H, Ph], 5.20 [s, 5H, C5H5], 3.72 [d, 2H, CH2, JHP
/
ꢀ
/
2
2
7.8 Hz], 2.16 [d, 3H, Me, JHP
4.62 [d, 2H, CH2, JHP
233.9 [t, Mꢁ
CO, 2JPC
5.7 Hz], 136.3ꢁ
ꢀ
/
8.3 Hz]. 13C{1H} (CDCl3): d
27.1 Hz], 193.3 [d, CÄ
O, 2JPC
ꢀ
/
9.4 Hz]. 13C{1H}
17.5 Hz], 165.1
2
/
ꢀ
/
/
ꢀ
/
(CDCl3): d 235.2 [t, Mꢁ
[CÄO], 134.1ꢁ
1JCP
16.9 Hz], 20.1 [d, Me, JCP
/
CO, JCP
ꢀ
/
/
128.0 [m, Ph], 95.4 [C5H5], 40.9 [d, CH2,
/
/
126.1 [m, Ph], 94.9 [C5H5], 27.6 [d, CH2,
1JPC
2JPP
ꢀ
/
28.5 Hz]. 31P{1H} (CDCl3): d 57.7 [d, PPh3,
ꢀ
/
ꢀ
/
33.3 Hz]. 31P{1H}
1
2
19 Hz], 47.3 [d, PPh2CH2C(O)Ph, JPP
2
ꢀ
/
ꢀ
/
19 Hz].
.
(CDCl3); d 55.6 [d, PPh2CH2C(O)NPh2, JPP
ꢀ18 Hz],
18 Hz]. nmax (CH2Cl2): n(CO)
/
2
nmax (CH2Cl2): n(CO) 1974, 1895; n(CÄ
/
O) 1684 cmꢃ1
41.3 [d, PMePh2, JPP
1972, 1892; n(CÄ
O) 1663 cmꢃ1
10d: Reaction time 14 days, yield 90%. 1H-NMR
(CDCl3): d 7.79ꢁ7.27 [m, 35H, Ph], 5.20 [s, 5H, C5H5],
ꢀ
/
/
.
3.5. Preparation of [Mo(CO)2{PPh2CHÄ
/
C(O)Ph-
P,O}(h5-C5H5)] (9)
/
2
3.65 [d, 2H, CH2, JHP
2
CO, JCP
ꢀ
7.8 Hz]. 13C{1H} (CDCl3): d
/
Triethylamine (19 ml, 0.135 mmol) was added to a
solution of 2a (74 mg, 0.133 mmol) in CH2Cl2 (10 ml).
The solution was stirred for 2 h, the solvent removed in
vacuo and the crude product recrystallised from
234.8 [t, Mꢁ
/
ꢀ
/
17.4 Hz], 165.0 [CÄ
/
O], 136.7ꢁ
/
1
126.8 [m, Ph], 95.2 [C5H5], 27.8 [d, CH2, JCP
ꢀ/16.8
Hz]. 31P{1H} (CDCl3): d 60.1 [d, PPh3, JPP
ꢀ18 Hz],
/
2
2
54.6 [d, PPh2CH2C(O)NPh2, JPP
ꢀ
/
18 Hz]. nmax
.
CH2Cl2ꢁ
mg (94%). Anal. Found (Calc for C27H21MoO3P×
4CH2Cl2): C 60.6 (60.4), H 4.21 (4.00)%. 1H-NMR
/
hexane to give orange crystals of 9. Yield 65
(CH2Cl2): n(CO) 1974, 1896; n(CÄ
/
O) 1663 cmꢃ1
/1/
3.7. Crystallography
(CDCl3): d 7.74ꢁ7.20 [m, 15H, Ph], 5.19 [d, 1H, PCH,
/
2JHP
ꢀ
/
1.2 Hz], 5.04 [s, 5H, C5H5]. 13C{1H} (CDCl3): d
4a: crystals suitable for an X-ray structural analysis
were grown from the slow diffusion of toluene into a
dichloromethane solution of 4a. C25H21BF4MoNO3P,
2
CO, JCP
253.2 [d, Mꢁ
2JCP
132.2ꢁ
1JCP
/
ꢀ
/
29.7 Hz], 242.7 [d, Mꢁ
/
CO,
30.1 Hz],
2
CO, JCP
ꢀ
/
4.1 Hz], 181.1 [d, Cꢀ
/
ꢀ
/
˚
0.71073 A, triclinic,
/
125.7 [m, Ph], 94.0 [C5H5], 45.6 [d, PCHÄ
/C,
Mꢀ
/
597.15, Tꢀ
/
173(2) K, lꢀ
/
ꢀ
/
69.7 Hz]. 31P{1H} (CDCl3):
d
68.4. nmax
space group P ꢁ
/
1, aꢀ
/
10.2215(7), bꢀ
/
10.9379(7), cꢀ
/

22
C.D. Andrews et al. / Journal of Organometallic Chemistry 665 (2003) 15ꢁ22
/
˚
11.0922(8) A, aꢀ
79.200(1)8, Uꢀ1211.51(14) A , Zꢀ
gcmꢃ3, mꢀ0.667 mmꢃ1, crystal size 2.0ꢄ
mm, 1.855u 527.518. 12695 reflections collected of
which 5507 were independent [Rint 0.0271] and 4310
observed (]2s). Final R indices R1ꢀ0.0313, wR2ꢀ
0.0702 [I ]2s(I)].
/
89.078(1), bꢀ
/
84.012(1), gꢀ
2, rcalc 1.637
0.2ꢄ0.2
/
References
3
˚
/
/
ꢀ
/
[1] (a) A. Bader, E. Lindner, Coord. Chem. Rev. 108 (1991) 27;
(b) C.S. Slone, D.A. Weinberger, C.A. Mirkin, Prog. Inorg.
Chem. 48 (1999) 233.
/
/
/
/
/
ꢀ
/
[2] P. Braunstein, F. Naud, Angew. Chem. Int. Ed. 40 (2001) 680.
[3] (a) S.-E. Bouaoud, P. Braunstein, D. Grandjean, D. Matt, D.
Nobel, Inorg. Chem. 25 (1986) 3765;
/
/
/
/
(b) P. Braunstein, D. Matt, D. Nobel, F. Balegroune, S.-E.
Bouaoud, D. Grandjean, J. Fischer, J. Chem. Soc. Dalton Trans.
(1988) 353;
9: crystals suitable for an X-ray structural analysis
were grown from the slow evaporation of a chloroform-
d solution of 9. C27H21MoO3P, Mꢀ
/
520.35, Tꢀ
/
170(2)
(c) P. Braunstein, Y. Chauvin, J. Nahring, A. DeCian, J. Fischer,
¨
˚
A. Tiripicchio, F. Ugozzoli, Organometallics 15 (1996) 5551;
(d) J. Andrieu, P. Braunstein, F. Naud, R.D. Adams, J.
Organomet. Chem. 601 (2000) 43.
K, lꢀ
aꢀ8.2520(1), bꢀ
2257.10(6) A , Zꢀ
mmꢃ1, crystal size 0.15ꢄ
27.488. A total of 34 621 reflections collected of which
5171 were independent [Rint 0.0436] and 4913 ob-
served (]2s). Final R indices R1ꢀ0.0340, wR2ꢀ
0.0868 [I ]2s(I)].
/0.71073 A, orthorhombic, space group P212121,
˚
/
/
14.3430(3), cꢀ
4, rcalc
1.531 g cmꢃ3, mꢀ
0.15ꢄ0.15 mm, 1.785
/
19.0700(2) A, Uꢀ
0.679
u 5
/
3
˚
/
ꢀ
/
/
[4] C.D. Andrews, A.D. Burrows, J.M. Lynam, M.F. Mahon, M.T.
Palmer, New J. Chem. 25 (2001) 824.
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/
/
[5] S. Al-Jibori, M. Hall, A.T. Hutton, B.L. Shaw, J. Chem. Soc.
Dalton Trans. (1984) 863.
ꢀ
/
[6] (a) N.G. Jones, M.L.H. Green, I.C. Vei, L.H. Rees, S.I. Pascu, D.
Watkin, A. Cowley, X. Morise, P. Braunstein, J. Chem. Soc.
Dalton Trans. (2002) 2491;
/
/
/
/
(b) N.G. Jones, M.L.H. Green, I. Vei, A. Cowley, X. Morise, P.
Braunstein, J. Chem. Soc. Dalton Trans. (2002) 1487.
[7] J.-M. Camus, D. Morales, J. Andrieu, P. Richard, R. Poli, P.
Braunstein, F. Naud, J. Chem. Soc. Dalton Trans. (2000) 2577.
[8] M. Abu Bakar, A. Hills, D.L. Hughes, G.J. Leigh, J. Chem. Soc.
Dalton Trans. (1989) 1417.
4. Supplementary material
[9] A.D. Burrows, N. Carr, M. Green, J.M. Lynam, M.F. Mahon,
M. Murray, B. Kiran, M.T. Nguyen, C. Jones, Organometallics
21 (2002) 3076.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 189988 and 189989 for
compounds 4a and 9, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge
[10] (a) D.A. Fletcher, R.F. McMeeking, D. Parkin, J. Chem. Inf.
Comput. Sci. 36 (1996) 746;
(b) F.H. Allen, O. Kennard, Chem. Des. Automat. News 8 (1993)
1, 31.
[11] L. Salsini, M. Pasquali, M. Zandomeneghi, C. Festa, P. Leoni, D.
Braga, P. Sabatino, J. Chem. Soc. Dalton Trans. (1990) 2007.
[12] W.A. Herrmann (Ed.), Synthetic Methods of Organometallic and
Inorganic Chemistry, vol. 8, Thieme, Stuttgart, 1996, p. 103.
[13] T.S. Piper, G. Wilkinson, J. Inorg. Nucl. Chem. 3 (1956) 104.
[14] J. Andrieu, P. Braunstein, A.D. Burrows, J. Chem. Res. S (1993)
380.
CB2 1EZ, UK (Fax:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.ca-
ꢂ44-1223-336033; e-mail:
/
m.ac.uk).