Reactions of rhenium and manganese carbonyl complexes with 1,8-bis(diphenylphosphino)naphthalene: Ligand chelation, C-H and C-P bond-cleavage reactions

Article abstract of DOI:10.1016/j.jorganchem.2008.05.001

Reaction of [Re₂(CO)₈(MeCN)₂] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three mono-rhenium complexes fac-[Re(CO)₃(κ¹:η¹-PPh₂C₁₀H₆)(PPh₂H)] (1), fac-[Re(CO)₃{κ¹:κ¹:η¹-(O)PPh₂C₁₀H₆(O)PPh(C₆H₄)}] (2) and fac-[ReCl(CO)₃(κ²-PPh₂C₁₀H₆PPh₂)] (3). Compounds 1-3 are formed by Re-Re bond cleavage and P-C and C-H bond activation of the dppn ligand. Each of these three complexes have three CO groups arranged in facial fashion. Compound 1 contains a chelating cyclometalated diphenylnaphthylphosphine ligand and a terminally coordinated PPh₂H ligand. Compound 2 consists of an orthometalated dppn-dioxide ligand coordinated in a κ¹:κ¹:η¹-fashion via both the oxygen atoms and ortho-carbon atom of one of the phenyl rings. Compound 3 consists of an unchanged chelating dppn ligand and a terminal Cl ligand. Treatment of [Mn₂(CO)₈(MeCN)₂] with a slight excess of dppn in refluxing toluene at 72 °C, gave the previously reported [Mn₂(CO)₈(μ-PPh₂)₂] (4), formed by cleavage of C-P bonds, and the new compound fac-[MnCl(CO)₃(κ²-PPh₂C₁₀H₆PPh₂)] (5), which has an unaltered chelating dppn and a terminal Cl ligand. In sharp contrast, reaction of [Mn₂(CO)₈(MeCN)₂] with slight excess of dppn at room temperature yielded the dimanganese [Mn₂(CO)₉{κ¹-PPh₂(C₁₀H₇)}] (6) in which the diphenylnaphthylphosphine ligand, formed by facile cleavage of one of the P-C bonds, is axially coordinated to one Mn atom. Compound 6 was also obtained from the reaction of [Mn₂(CO)₉(MeCN)] with dppn at room temperature. The XRD structures of complexes 1-3, 5, 6 are reported.

Full text of DOI:10.1016/j.jorganchem.2008.05.001

Journal of Organometallic Chemistry 693 (2008) 2657–2665
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reactions of rhenium and manganese carbonyl complexes with
1,8-bis(diphenylphosphino)naphthalene: Ligand chelation, C–H
and C–P bond-cleavage reactions
a
a
a
a
Shariff E. Kabir a, , Faruque Ahmed , Shishir Ghosh , Mohammad R. Hassan , Muhammad S. Islam ,
*
Ayesha Sharmin a, Derek A. Tocher b, , Daniel T. Haworth , Sergey V. Lindeman , Tasneem A. Siddiquee ,
c
c
d
*
Dennis W. Bennett d, Kenneth I. Hardcastle e
a Department of Chemistry, Jahangirnagar University, Savar, Dhaka-1342, Bangladesh
b Department of Chemistry, University College London, 20 Gordon Street, London WC1H OAJ, UK
c Department of Chemistry, Marquette University, Milwaukee, WI 53201-1881, USA
d Department of Chemistry, University of Wisconsin-Milwaukee, P.O. Box 413, WI 53211-3029, USA
e Department of Chemistry, Emory University, Atlanta, GA 30322, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of [Re2(CO)8(MeCN)2] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three
mono-rhenium complexes fac-[Re(CO)3(j1 1-PPh2C10H6)(PPh2H)] (1), fac-[Re(CO)3{j1 j1 g1
:g : : -
Received 11 March 2008
Received in revised form 23 April 2008
Accepted 4 May 2008
(O)PPh2C10H6(O)PPh(C6H4)}] (2) and fac-[ReCl(CO)3(j
2-PPh2C10H6PPh2)] (3). Compounds 1–3 are formed
by Re–Re bond cleavage and P–C and C–H bond activation of the dppn ligand. Each of these three com-
plexes have three CO groups arranged in facial fashion. Compound 1 contains a chelating cyclometalated
diphenylnaphthylphosphine ligand and a terminally coordinated PPh2H ligand. Compound 2 consists of
Available online 7 May 2008
Keywords:
Dirhenium and dimanganese carbonyl
complexes
1,8-Bis(diphenylphosphino)naphthalene
Bond-cleavage (C–P and C–H) reactions
Chelates
an orthometalated dppn-dioxide ligand coordinated in a j1 j1 1-fashion via both the oxygen atoms and
: :g
ortho-carbon atom of one of the phenyl rings. Compound 3 consists of an unchanged chelating dppn
ligand and a terminal Cl ligand. Treatment of [Mn2(CO)8(MeCN)2] with a slight excess of dppn in refluxing
toluene at 72 °C, gave the previously reported [Mn2(CO)8(
and the new compound fac-[MnCl(CO)3(
2-PPh2C10H6PPh2)] (5), which has an unaltered chelating dppn
and a terminal Cl ligand. In sharp contrast, reaction of [Mn2(CO)8(MeCN)2] with slight excess of dppn at
room temperature yielded the dimanganese [Mn2(CO)9{
1-PPh2(C10H7)}] (6) in which the diphenylnaph-
l-PPh2)2] (4), formed by cleavage of C–P bonds,
j
X-ray structure
j
thylphosphine ligand, formed by facile cleavage of one of the P–C bonds, is axially coordinated to one Mn
atom. Compound 6 was also obtained from the reaction of [Mn2(CO)9(MeCN)] with dppn at room temper-
ature. The XRD structures of complexes 1–3, 5, 6 are reported.
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
example, Bruce and coworkers reported three tetraruthenium
compounds,
[Ru4( -H)(CO)11
(CO)9( 4-C6H4){
[Ru3( -H)(CO)8{
[Ru4(
3-C6H4){
4-P(nap)PPh2}] and one triruthenium compound
l3-PPh2(nap)PPh(C6H4)}] (nap = 1,8-C10H6) from
l
-H)(
l
-CO)3(CO)7{
l
3-PPh2(nap)PPh(C6H4)}],
The synthesis and reactivity of transition metal carbonyl com-
plexes bearing diphosphine ligands continue to excite interest,
both from a synthetic point of view due to their potential applica-
bility to effect organic transformations [1–4], and their possible
involvement in homogeneous catalytic processes [5,6]. Late transi-
tion metal systems with chelating diphosphine ligands such as 1,8-
bis(diphenylphosphino)naphthalene with a rigid C3-backbone [7,8]
have been reported to be active catalysts in CO/ethylene co-poly-
merization [9]. The reactivity of this ligand with polynuclear tran-
sition metal carbonyl compounds have been recently investigated
by the Bruce [10–12] and Richmond [13,14] research groups. For
l
l
l
(
l
l
l
-PPh(nap)PPh2}], and [Ru4(
l
-CO)-
reactions of [Ru3(CO)12] and 1,8-bis(diphenylphosphino)naphtha-
lene at elevated temperatures [10]. These compounds were formed
by the aryl C–H and C–P bond-cleavage reactions of the ligand.
They also reported that [Os3(CO)12] reacts with 1,8-bis(diphenyl-
phosphino)naphthalene at 110 °C to give the triosmium com-
pounds [Os3(
(CO)8{ 3-PPh2(nap)PPh(C6H4)}], and the dinuclear [Os2(CO)5-
-PPh2)( -PPh2(nap))] (Scheme 1) [11]. The triosmium compounds
l-H)2(CO)6{l3-PPh2(nap)PPh(C6H4)}2] and [Os3(l-H)-
l
(l
l
are formed by metallation of a Ph group of dppn, while the dinu-
clear compound is formed by cleavage of a C–P bond of the ligand.
With a view to restrict the subsequent reactions to the C10 ring,
* Corresponding authors.
E-mail address: skabir_ju@yahoo.com (S.E. Kabir).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.05.001

2658
S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
(CO)4
Os
Os
Os (CO)4
(OC)3
PPh2
THF,
RT
Ph
Me3NO
(OC)2 Os
P
Ph2P
PPh2
Toluene
110 oC
Os(CO)3
Os
(OC)2
[Os3(CO)12]
+
P
Ph2
H
+
(CO)2
Os
Ph
Ph
H
H
PPh2
P
P
(OC)3Os
Os (CO)2
(CO)2
Os
+
(OC)2 Os
P
P
Ph2
P
Ph2
Ph2
Scheme 1.
they investigated the reactions of 1,8-bis(dimethylphosphino)-
naphthalene with [Ru3(CO)12 and [Ru3(CO)10 -dppm)] and
obtained [Ru3(CO)12Àn{PMe2(nap)}n] (n = 1–3) and [Ru3(CO)9-
-dppm){PMe2(nap)}], respectively [12]. However, it is interesting
recorded on a Bruker DPX 400 spectrometer. Elemental analyses
were performed by BCSIR Laboratories, Dhaka. Fast atom bombard-
ment mass spectra were obtained on a JEOLSX-102 spectrometer
using 3-nitrobenzyl alcohol as matrix and CsI as calibrant.
]
(l
(l
to note that a cluster containing an unaltered dppn ligand was not
detected in any of the above reactions. Very recently, Richmond
et al. have investigated the reactions of 1,8-bis(diphenylphos-
phino)naphthalene with the hydride-bridged ruthenium cluster
[Ru4(l-H)4(CO)12] and the cobalt cluster [PhCCo3(CO)9] and ob-
tained products containing both unaltered and activated dppn li-
2.1. Reaction of [Re2(CO)8(MeCN)2] with dppn
A toluene solution (35 mL) of [Re2(CO)8(MeCN)2] (150 mg,
0.15 mmol) and dppn (150 mg, 0.30 mmol) was heated to reflux
for 1 h and 15 min. The solvent was removed by rotary evaporation
and the residue chromatographed by TLC on silica gel. Elution with
hexane/CH2Cl2 (4:1, v/v) developed three bands. The first band
gands [13,14]. For instance, the ruthenium cluster afforded
[Ru3(
whereas the cobalt cluster yielded [PhCCo3(CO)8{PPh2(1-C10H7)}]
and [PhCCo3(CO)4( -CO)3(
2-dppn)] [14] under the same experi-
l-H)4(CO)10(j
2-dppn)] as the sole isolable product [13];
gave fac-[Re(CO)3(j1 1-PPh2C10H6)(PPh2H)] (1) (23 mg, 14%) as
:g
l
j
colorless crystals after recrystallization from hexane/CH2Cl2 at
mental conditions. To our knowledge, however, no examples have
been reported in the literature concerning the reactivity between
1,8-bis(diphenylphosphino)naphthalene and group 7 transition
metal carbonyl complexes. We thus decided to investigate the reac-
tivity of 1,8-bis(diphenylphosphino)naphthalene with the labile
complexes [Re2(CO)8(MeCN)2], [Mn2(CO)9(MeCN)] and [Mn2(CO)8-
(MeCN)2] and the results are described in the present paper.
4 °C. Anal. Calc. for C37H27O3P2Re: C, 57.88; H, 3.54. Found: C,
58.22; H, 3.71%. IR (
mCO, CH2Cl2): 2011 vs, 1942 vs, 1900 vs
cmÀ1 1H NMR (CDCl3): d 7.92 (d, J = 7.8 Hz, 1H), 7.65 (t, J =
.
7.4 Hz, 1H), 7.52 (d, J = 7.8 Hz, 1H), 7.45 (m, 7H), 7.32 (m, 4H),
7.21 (m, 3H), 6.97 (m, 7H), 6.52 (d, J = 7.4 Hz, 1H), 6.49 (d, J =
7.4 Hz, 1H), 4.92 (dd, JP–H = 357.1, 9.3 Hz, 1H). 31P–{1H} NMR
(CDCl3): d 31.5 (s), 1.7 (s). MS (FAB): m/z 768 (M+). The second band
afforded
fac-[Re(CO)3{j1
:
j1
:g
1-OPPh2C10H6OPPh(C6H4)}]
(2)
2. Experimental
(19 mg, 11%) as colorless crystals after recrystallization from hex-
ane/CH2Cl2 at 4 °C. Anal. Calc. for C37H25O5P2Re: C, 55.71; H,
All the reactions were performed under a nitrogen atmosphere
using standard Schlenk techniques. Solvents were dried and dis-
tilled prior to use by standard methods. Bis(diphenylphos-
phino)naphthalene (dppn), a gift from Prof. Michael G. Richmond,
was prepared according to the known method [15] and used as re-
ceived. Me3NO Á 2H2O was purchased from Lancaster and water
was removed using a Dean-Stark apparatus by azeotropic distilla-
tion from benzene and the anhydrous Me3NO was stored under
nitrogen. The starting complexes [Re2(CO)8(MeCN)2] [16],
[Mn2(CO)9(MeCN)] [17] and [Mn2(CO)8(MeCN)2 [17] were prepared
according to published procedures. Infrared spectra were recorded
on a Shimadzu FTIR 8101 spectrophotometer. 1H NMR spectra were
3.16. Found: C, 55.92; H, 3.34%. IR (
mCO, CH2Cl2): 1998 vs, 1881
vs, 1860 vs cmÀ1 1H NMR (CDCl3): d 8.07 (m, 2H), 7.89 (m, 2H),
.
7.65 (d, J = 7.2 Hz, 1H), 7.60 (d, J = 7.2 Hz, 1H), 7.35 (t, J = 7.2 Hz,
1H), 7.37(m, 4H), 7.21 (m, 9H), 7.17 (t, J = 7.2 Hz, 1H), 6.84 (d,
J = 6.4 Hz, 1H), 6.81 (d, J = 7.4 Hz, 1H), 6.74 (m, 1H), 6.65 (t,
J = 7.2 Hz, 1H). 31P–{1H} NMR (CDCl3): d 69.0 (s), 38.7 (s). MS
(FAB): m/z 798 (M+). The third band yielded fac-[Re-
(Cl)(CO)3(PPh2C10H6PPh2)] (3) (71 mg, 40%) as colorless crystals
after recrystallization from hexane/CH2Cl2 at 4 °C. Anal. Calc. for
C
37H26O3Cl1P2Re2: C, 55.40; H, 3.27. Found: C, 55.67; H, 3.38%. IR
CO, CH2Cl2): 2070 s, 2012 vs, 1966 s cmÀ1 1H NMR (CDCl3): d
8.05 (m, 2H), 7.63 (m, 4H), 7.37 (m, 10H), 7.11 (t, J = 7.2 Hz, 2H),
(m
.

S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
2659
6.96 (t, J = 7.2 Hz, 4H), 6.83 (m, 4H). 31P–{1H} NMR (CDCl3): d 8.9(s).
2.3. Reaction of [Mn2(CO)9(MeCN)] with dppn
CH2Cl2 solution (30 mL) of [Mn2(CO)9(MeCN)] (160 mg,
MS (FAB): m/z 802 (M+).
A
0.40 mmol) and dppn (198 mg, 0.40 mmol) was stirred at room
temperature for 48 h. The solvent was removed under reduced
pressure and the residue chromatographed by TLC on silica gel.
Elution with hexane/CH2Cl2 (7:3, v/v) developed four bands. The
last band was unreacted starting material while the second band
2.2. Reaction of [Mn2(CO)8(MeCN)2] with dppn
2.2.1. At 72 °C
A toluene solution (35 mL) of [Mn2(CO)8(MeCN)2] (180 mg,
0.43 mmol) and dppn (215 mg, 0.43 mmol) was heated at 72 °C
for 5 h. After removal of the solvent under reduced pressure, the
residue was chromatographed as above to develop two bands.
gave [Mn2(CO)9{j
1-PPh2(C10H7)}] (6) (35 mg, 27%) as yellow crys-
tals after recrystallization from hexane/CH2Cl2 at 4 °C. The other
two bands gave too little product for complete characterization.
The first band gave the known compound [Mn2(CO)8(l-PPh2)2]
(4) (29 mg, 10%) as pale yellow crystals after recrystallization from
2.4. X-ray structure determinations
hexane/CH2Cl2 at 4 °C. The second band afforded fac-
[Mn(Cl)(CO)3(j
1-PPh2C10H6PPh2)] (5) (66 mg, 23%) as colorless
Single crystals were mounted on fibres and diffraction data col-
lected at low temperature (see Table 1) on Bruker AXS SMART APEX
CCD diffractometers using Mo Ka radiation (k = 0.71073 Å). Data col-
crystals after recrystallization from hexane/CH2Cl2 at 4 °C. Anal.
Calc. for C37H26ClO3MnP2: C, 66.23; H, 3.91. Found: C, 66.39; H,
4.24%. IR (m .
CO, CH2Cl2): 2067 s, 2013 vs, 1968 s cmÀ1 1H NMR
lection, indexing and initial cell refinements were all done using SMART
[18] software. Data reduction were done with SAINT [19] software and
the SADABS programme [20] was used to apply empirical absorption
corrections. The structures were solved by direct methods [21] and
refined by full-matrix least-squares [22]. All non-hydrogen atoms
were refined anisotropically and hydrogen atoms were included
using a riding model. Scattering factors were taken from Interna-
tional Tables for X-ray Crystallography [23]. Additional details of data
collection and structure refinement are given in Table 1.
(CDCl3): d 8.04 (m, 2H), 7.79 (m, 4H), 7.39 (m, 10H), 7.11 (m,
2H), 6.95 (m, 4H), 6.86 (m, 4H). 31P–{1H} NMR (CDCl3): d 49.3 (s).
MS (FAB): m/z 670 (M+).
2.2.2. At room temperature
A CH2Cl2 solution (50 mL) of [Mn2(CO)8(MeCN)2] (160 mg,
0.38 mmol) and dppn (191 mg, 0.38 mmol) was stirred at room
temperature for 45 h. The solvent was removed under reduced
pressure and the residue chromatographed as above to give one
major and several minor bands. The major band gave
[Mn2(CO)9{
after recrystallization from hexane/CH2Cl2 at 4 °C. Anal. Calc. for
31H17O9Mn2P: C, 55.22; H, 2.54. Found: C, 55.40; H, 2.76%. IR
j
1-PPh2(C10H7)}] (6) (30 mg, 12%) as yellow crystals
3. Results and discussion
C
3.1. Formation of mononuclear rhenium complexes by C–P and C–H
bond activation in dppn
(m .
CO, CH2Cl2): 2090 s, 2009 s, 1992 vs, 1967 m, 1933 m cmÀ1 1H
NMR (CDCl3): d 7.94–7.83 (m, 5H), 7.62–7.43 (m, 12H). 31P–{1H}
NMR (CDCl3): d 74.3 (s). MS (FAB): m/z 674 (M+). The contents of
the minor bands were too small for complete characterization.
Treatment of [Re2(CO)8(MeCN)2] with two equivalents of dppn
in refluxing toluene, followed by chromatographic separation, lead
Table 1
Crystallographic data and structure refinementa for 1, 2, 3, 5 and 6
1
2
3
5
6
Empirical formula
Formula weight
T (K)
C
37H27O3P2Re
C38H27Cl2O5P2Re
882.64
150(2)
C37H26ClO3P2Re
802.17
173(2)
C37H26ClMnO3P2
670.91
293(2)
C31H17Mn2O9P
674.30
150(2)
767.73
100(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Monoclinic
C2/c
19.1751(3)
18.7407(3)
18.4101(3)
90
113.0020(10)
90
6089.74(17)
8
Triclinic
P1
Triclinic
P1
10.4072(4)
14.9325(5)
20.3603(7)
83.187(2)
88.310(2)
86.761(2)
3135.91(19)
4
1.699
Triclinic
P1
Orthorhombic
Pbca
15.9421(12)
18.0361(14)
19.8983(15)
90
90
90
5721.4(8)
8
1.566
ꢀ
ꢀ
ꢀ
10.8628(8)
11.8435(9)
14.0293(11)
94.7370(10)
109.1060(10)
90.7270(10)
1698.2(2)
10.2672(6)
14.7815(9)
20.0466(12)
83.1140(10)
88.3270(10)
86.7250(10)
3014.7(3)
a
(°)
b (°)
(°)
c
Volume (Å3)
Z
2
4
DCalc (Mg/m3)
1.675
9.093
1.726
3.874
1.478
0.671
l
(Mo K
a
) (mmÀ1
)
9.625
0.994
F(000)
3024
868
1576
1376
2720
Crystal size (mm3)
h Range (°)
0.20 Â 0.14 Â 0.12
3.44–61.41
À21 6 h 6 19
0 6 k 6 20
0 6 l 6 20
25134
0.44 Â 0.40 Â 0.34
1.73–28.26
À14 6 h 6 14
À15 6 k 6 15
À18 6 l 6 18
15004
0.28 Â 0.16 Â 0.13
2.19–65.75
À11 6 h 6 10
À17 6 k 6 17
À23 6 l 6 23
14154
0.46 Â 0.24 Â 0.08
1.39–28.26
À13 6 h 6 13
À19 6 k 6 19
À26 6 l 6 26
26782
0.44 Â 0.42 Â 0.12
1.99–28.29
À20 6 h 6 21
À23 6 k 6 23
À26 6 l 6 26
48038
Index ranges
Reflections collected
Independent reflections [R(int)]
Maximum and minimum transformation
Data/restraints/parameters
Goodness-of-fit on F2
4565 [0.0253]
0.4083 and 0.2635
4565/36/471
1.166
7794 [0.0210]
0.3526 and 0.2805
7794/0/434
1.030
6165 [0.0166]
0.3676 and 0.1736
6165/0/788
1.122
13880 [0.0245]
0.9483 and 0.7477
13880/0/793
1.036
6974 [0.0299]
0.6688 and 0.8900
6974/0/388
1.037
Final R indices [I > 2
r
(I)]
R1 = 0.0196
wR2 = 0.0484
R1 = 0.0198
wR2 = 0.0485
0.666 and À0.378
R1 = 0.0250
wR2 = 0.0621
R1 = 0.0258
wR2 = 0.0625
1.492 and À1.736
R1 = 0.0589
wR2 = 0.1635
R1 = 0.0735
wR2 = 0.2149
1.346 and À3.245
R1 = 0.0429
wR2 = 0.1001
R1 = 0.0556
wR2 = 0.1064
0.592 and À0.454
R1 = 0.0302
wR2 = 0.0741
R1 = 0.0355
wR2 = 0.0768
0.439 and À0.214
R indices (all data)
Largest difference peak and hole (e ÅÀ3
)
a
Details in common: X-radiation, Mo Ka
(k = 0.71073 Å), refinement method: full-matrix least-squares on F2.

2660
S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
Ph2P
PPh2
HPh2P
OC
Ph2
P
Toluene
110 oC
Re2(CO)8(MeCN)2
+
Re
OC
CO
1
+
CO
CO
Re
CO
O
O
Cl
Ph P
+
PPh2
Ph2P
PPh2
CO
Re
CO
3
OC
2
Scheme 2.
to the formation of three new compounds fac-[Re(CO)3(j1
:
g1
-
the average Re–CO bond distances in fac-[ReCl(CO)3{j1
-
PPh2C10H6)(PPh2H)] (1), fac-[Re(CO)3{j1 1-OPPh2C10H6OPPh-
:
j1
:g
NC3H3N(CH3)}2] {1.917(3) Å} and fac-[ReCl(CO)3{j
1-NC3H3S}2]
(C6H4)}] (2) and fac-[Re(Cl)(CO)3(PPh2C10H6PPh2)] (3) in 14%, 11%
and 40% yields, respectively (Scheme 2). All compounds have been
characterized by a combination of IR, NMR, mass spectral data, ele-
mental analysis and single crystal X-ray diffraction studies. Forma-
tion of these mononuclear compounds (1–3) may proceed from
[Re2(CO)8(MeCN)(dppn)] which can undergo bond cleavage form-
ing [Re(CO)4(dppn)] and [Re(CO)4(MeCN)]. The later compound
can reform the dimer and the former compound can give com-
pound 1 by C–P bond cleavage of the chelating dppn with cyclo-
metalation of the naphthyl group at C(1) (Fig. 1) and loss of one
CO ligand. The hydride of PPh2H comes from the formation of com-
pound 2 with orthometallation to Re of a phenyl group of PPh2.
Also O2 insertion (oxidative addition) between the Re–P bonds fol-
lowed by Re–C(1) bond cleavage and P–C(1) (Fig. 1) bond forma-
tion yields compound 2.
{1.914(7) Å} [24,25].
The spectroscopic data of 1 are consistent with the solid-state
structure. The infrared spectrum display three bands in the car-
bonyl stretching region indicating the fac arrangement of the car-
bonyls, similar to those observed for fac-[Re(CO)3L2X] type
compounds [24–28]. In addition to the usual phenyl and naphthyl
The molecular structure of 1 is shown in Fig. 1 and selected
bond distances and angles are listed in the caption. The compound
contains a single rhenium atom with three carbonyl groups, a
diphenylphosphine and a cyclometalated naphthyldiphenylphos-
phine ligand. The coordination geometry at the Re atom is a dis-
torted octahedron with three carbonyl ligands arranged in a
facial fashion. The distortion from octahedral coordination geome-
try is evident from reduction of the C–Re–P angle from 90° in the
idealized polyhedron to 79.04(8)° in 1. The trans angles about rhe-
nium range from 168.62(9)° to 172.48(9)° which are comparable to
the corresponding angles in fac-[ReCl(CO)3{
{range from 175.44(14)° to 178.99(13)°} [24] and fac-
[ReCl(CO)3{
1-NC3H3S}] {range from 174.44(18)° to 179.27(19)°} [25].
j
1-NC3H3N(CH3)}2]
j
The Re(1)–C(1) bond distance {2.225(3) Å} is shorter than those
observed in Re-cyclopentadienyl complexes {2.245–2.405 Å} [26].
The Re–P bond distances {Re(1)–P(1) = 2.4204(7) and Re(1)–
P(2) = 2.4456(7) Å} are comparable to the Re–P bond distances in
Fig. 1. Molecular structure of fac-[Re(CO)3(j1 1-PPh2C10H6)(PPh2H)] 1 showing
:g
50% probability thermal ellipsoids. Hydrogen atoms except the one attached to
the phosphorus atom are omitted for clarity. Selected bond lengths (Å) and
angles (°): Re(1)–P(1) = 2.4204(7), Re(1)–P(2) = 2.4456(7), Re(1)–C(1) = 2.225(3),
Re(1)–C(11) = 1.941(3), Re(1)–C(12) = 1.951(3), Re(1)–C(13) = 1.960(3), C(1)–
[Re2(l-H)2(CO)6(l-dppm)] {2.457(4)°, 2.449(4)°} [27]. The five-
membered chelate metallocycle ring is nearly coplanar and the ori-
entation of the phenyl rings is unusual and presumably would not
persist in solution. The carbonyl groups assume a fac geometry
with a longer average Re–CO bond distance of 1.950(9) Å than
Re(1)–P(1) = 79.04(8),
C(1)–Re(1)–P(2) = 82.67(7),
P(1)–Re(1)–P(2) = 87.95(2),
C(11)–Re(1)–C(1) = 86.02(11), C(12)–Re(1)–C(1) = 171.91(11), C(13)–Re(1)–C(1) =
93.81(12), C(11)–Re(1)–P(1) = 91.19(9), C(12)–Re(1)–P(1) = 92.98(9), C(13)–Re(1)–
P(1) = 172.48(9).

S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
2661
proton resonances in the aromatic region d 7.92–6.50, the 1H NMR
spectrum shows a doublet of doublets at d 4.93 (integrating to 1H)
assigned to the PH proton of the diphenylphosphine ligand. The
31P{1H} NMR spectrum displays two equal intensity singlets at d
31.5 and 1.7, assigned to the cyclometalated naphthyldiphenyl-
phosphine and diphenylphosphine ligands, respectively. The mass
spectrum of 1 shows a molecular ion at m/z 768 together with frag-
mentation peaks due to the successive loss of three carbonyl
groups.
The molecular structure of 2 is shown in Fig. 2 and selected
bond distances and angles are listed in caption. The compound
contains a single rhenium atom with three carbonyl groups and
an orthometalated bis(diphenylphosphino)naphthalenedioxide li-
gand. The coordination geometry at the Re atom is also a distorted
octahedron with three carbonyl ligands arranged in a facial fashion.
The distortion from octahedral coordination geometry is evident
from reduction of the O–Re–O angle from 90° in the idealized poly-
hedron to 74.12(8)° in 2. An interesting feature of the structure is
the coordination of the dppn-dioxide through both the oxygen
atoms as well as the orthometalated ligand. To the best of our
knowledge, such a transformation of dppn on a metal center is
unprecedented. In order to allow the oxygen atoms to be coordi-
nated to the Re center the naphthalene unit is considerably dis-
torted (deviations from planarity in the range 0.3 Å) in
comparison to the free ligand. The phosphorus atoms lie À0.97 Å,
P(1) and 1.11 Å, P(2) outside the least-squares plane of the naph-
thalene ring system, the torsion angle P(1)–C(16)Á Á ÁC(22)–P(2) is
54.5°. The Re–C bond distance, 2.169(3) Å, is significantly shorter
than those observed in 1. The Re–O bond distances, Re(1)–O(5)
2.175(2), Re(1)–O(4) 2.197(2) Å, are comparable to the Re–O bond
apparent triplets at d 7.17 and 6.65 (each integrating to 1H),
assignable to the orthometalated phenyl ring. As expected the
31P{1H} NMR exhibits two equal intensity singlets at d 69.0 and
38.6 indicating that the 31P nuclei are non-equivalent. The mass
spectrum contains the appropriate molecular ion peak (M+) for
the molecular mass of 798 Da.
Complex 3 crystallized with two molecules per asymmetric
unit. All molecules in the structure are separated by normal van
der Waals distances and there are no anomalously close intermo-
lecular contacts. The respective bond lengths and angles in the
two molecules show only minor variations. The structure of one
of these molecules is shown in Fig. 3 and selected bond distances
are listed in the caption. The molecule consists of a single rhenium
atom with three carbonyl groups, a chelating dppn ligand and a
terminally coordinated Cl ligand, which was contributed by the
solvent (CH2Cl2). The coordination geometry of the Re atom can
be described as a distorted octahedron with three carbonyl ligands
arranged in a facial fashion. The distortion from octahedral coordi-
nation geometry is evident from reduction of the P–Re–P angle
from 90° in the idealized polyhedron to 82.50(11)° in 3 which is
comparable with the P–Mo–P angle {81.267(13)°} in [Mo2-
(CO)4(dppn)] [30]. The basic structure of 3 is very similar to that
of the recently reported single rhenium compounds fac-
[ReCl(CO)3{j j
1-NC3H3N(CH3)}2] [24] and fac-[ReCl(CO)3{ 1-C3H3S}2]
[25]. A six-membered central ring in an envelope [1,3-biplanar]
conformation was observed. The atoms P(1), C(16), C(25), C(24)
and P(2) are approximately coplanar (mean deviation from the
plane 0.024), the deviation of Re from the ring being 1.25. A copla-
nar arrangement of the naphthalene ring and the metal would
necessitate considerable widening of the angles P(1)–C(16)–C(25)
(125.6(9)°) C16–C25–C24 (128.7(10)°) and P(2)–C(24)–C(25)
(126.4(8)°) and result in increased strain. The out-of-plane distor-
tion of the molecule can be seen from the torsion angles P(1)–
C(16)–C(25)–C(24) 0(2)° and P(2)–C(24)–C(25)–C(16) À5(2)°. The
carbonyl groups assume a fac geometry with two longer Re–CO
distance, 2.203(6) Å, in Re(CO)4[l-(E)-RC@C(CO2Et)]Re(CO)4 [29].
The spectroscopic data of 2 are fully consistent with the solid-
state structure. The pattern of the infrared spectrum of 2 in the car-
bonyl region is very similar to those of the fac-[Re(CO)3L2X] type
compounds which have been characterized by X-ray diffraction
studies [29–33]. The aromatic region of the 1H NMR spectrum con-
tains five multiplets at d 8.07, 7.89, 7.57–7.38, 7.21 and 6.85-6.69
are due to the phenyl and naphthyl ring protons of the oxygenated
dppn ligand besides this two doublets at d 7.65 and 7.60 and two
bond
distances
{C(1)–Re(1) 1.979(16)
and
C(3)–Re(1)
1.969(19) Å} and a significantly shorter Re–CO bond distance of
C(2)–Re(1) 1.909(14) Å, trans to the terminally coordinated chlo-
ride ligand, is comparable to the similar Re–CO bond distances in
Fig. 2. Molecular structure of fac-[Re(CO)3{j1 j1 1-OPPh2C10H6OPPh(C6H4)}] (2) showing 50% probability thermal ellipsoids. Hydrogen atoms are omitted for clarity.
: :g
Selected bond lengths (Å) and angles (°): Re(1)–C(1) = 1.876(3), Re(1)–C(2) = 1.958(3), Re(1)–C(3) = 1.889(3), Re(1)–C(4) = 2.169(3), Re(1)–O(5) = 2.175(2), Re(1)–
O(4) = 2.197(2), P(1)–O(4) = 1.520(2), P(2)–O(5) = 1.506(2), C(1)–Re(1)–C(4) = 98.54(12), C(3)–Re(1)–C(4) = 92.90(12), C(2)–Re(1)–C(4) = 173.61(12), C(2)–Re(1)–
O(5) = 91.48(11), C(4)–Re(1)–O(5) = 82.15(9), C(1)–Re(1)–O(4) = 99.01(11), C(2)–Re(1)–O(4) = 98.49(11), C(4)–Re(1)–O(4) = 80.29(9), O(5)–Re(1)–O(4) = 74.12(8).

2662
S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
Fig. 3. Molecular structure of fac-[ReCl(CO)3(PPh2C10H6PPh2)] (3) showing 35% probability thermal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond lengths
(Å) and angles (°): C(1)–Re(1) = 1.979(16), C(2)–Re(1) = 1.909(14), C(3)–Re(1) = 1.969(19), Cl(1)–Re(1) = 2.495(4), P(1)–Re(1) = 2.459(4), P(2)–Re(1) = 2.446(3), P(2)–Re(1)–
P(1) = 82.50(11), P(2)–Re(1)–Cl(1) = 85.76(11), P(1)–Re(1)–Cl(1) = 83.65(12).
fac-[ReCl(CO)3{
j
1-NC3H3N(CH3)}2] {1.908(14) Å} [24] and fac-
3.2. Formation of mono- and dimanganese complexes, C–P bond
activation in dppn
[ReCl(CO)3{
j
1-NC3H3S}2] {1.915(8) Å} [25]. The reason for length-
ening the other two Re–CO bond distances is probably due the
trans effect of the two P atoms of the chelating dppn ligand.
The spectroscopic data of 3 are consistent with the solid-state
structure. The infrared spectrum displays three bands in the car-
bonyl stretching region similar to those observed for compounds
1 and 2. The 1H NMR spectrum of 3 displays four multiplets at d
8.05, 7.63, 7.37 and 6.83 and two triplets at d 7.11 and 6.96 due
to the phenyl and naphthyl ring protons of the chelating dppn li-
gand. The mass spectrum of 3 exhibits a molecular ion peak at
m/z 802, and fragmentation peaks due to the successive loss of
three carbonyl groups.
Reaction of [Mn2(CO)8(MeCN)2] with slight excess of dppn in
refluxing toluene, followed by chromatographic separation, lead
to the formation of
(CO)3(PPh2C10H6PPh2)] (5) along with the known compound
[Mn2(CO)8( -PPh2)2] (4) in 10 and 23% yields, respectively (Scheme
a
new compound fac-[Mn(Cl)-
l
3). Compound 4 was previously characterized by spectroscopic
data and single crystal X-ray diffraction studies [31]. We have
characterized 4 by comparing the spectroscopic data with those re-
ported previously, and the new compound 5 by a combination of
spectroscopic data and single crystal X-ray diffraction studies.
CO
Ph2P
PPh2
OC
CO
Mn
CO
PPh2
CO
OC
Toluene
72 oC
Mn2(CO)8(MeCN)2
+
Ph2P
Mn
CO
OC
CH2Cl2 RT
4
+
CO
CO
OC
Mn
OC
OC
CO
OC
CO
CO
Mn
CO
Mn
Cl
CO
PPh2
PPh2
Ph2P
OC
6
5
Scheme 3.

S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
2663
Fig. 4. Molecular structure of fac-[MnCl(CO)3(PPh2C10H6PPh2)] (5) showing 50% probability thermal ellipsoids. Selected bond lengths (Å) and angles (°): Mn(1)–
C(1) = 1.793(2), Mn(1)–C(3) = 1.825(2), Mn(1)–C(2) =1.828(2), Mn(1)–P(2) = 2.3256(6), Mn(1)–P(1) = 2.3300(6), Mn(1)–Cl(1) = 2.3978(6), P(2)–Mn(1)–P(1) = 84.01(2), P(2)–
Mn(1)–Cl(1) = 86.20(2), P(1)–Mn(1)–Cl(1) = 92.22(2).
The crystal structure of 5 is isomorphous with that of 3, and the
molecular structure of one of the two molecules in the asymmetric
unit is shown in Fig. 4 with selected bond distances and angles in
the caption. The coordination geometry at the Mn atom is closely
similar to that already discussed for compound 3. For example,
the distortion from octahedral coordination geometry at the metal
is evident from the P–Mn–P angle, 82.50(11)°, comparable with the
P–Re–P angle {81.267(13)°} in 3. The distortions of the ligands dis-
cussed for 3 are also manifest in 5. The only truly significant differ-
ences between the two structures are in the bonds to the ligating
atoms. The carbonyl groups exhibit two longer Mn–CO bond dis-
tances {Mn(1)–C(3) 1.825(2) and Mn(1)–C(2) 1.828(2) Å} and one
shorter Mn–CO bond distance of Mn(1)–C(1) 1.793(2) Å, trans to
the terminally coordinated chloride ligand. These distances are con-
sistently shorter that those observed in 3 by ca. 0.11–0.15 Å. A sim-
ilar systematic shortening is seen in the bond lengths to the ligating
chlorine and phosphorus atoms. These differences are consistent
with the well known covalent radii for manganese and rhenium.
The spectroscopic data for 5 are consistent with the solid-state
structure. The infrared spectrum shows three bands in the
Fig. 5. Molecular structure of [Mn2(CO)9{j
1-PPh2(C10H7)}] (6) showing 50% probability thermal ellipsoids. Selected bond lengths (Å) and angles (°): Mn(1)–C(1) = 1.8107(16),
Mn(1)–C(3) = 1.8472(17), Mn(1)–Mn(2) = 2.9124(3), Mn(2)–P(1) = 2.2706(4), Mn(2)–C(7) = 1.8349(16), Mn(2)–C(8) = 1.8429(16), P(1)–Mn(2)–Mn(1) = 176.625(13), C(1)–
Mn(1)–Mn(2) = 178.63(5), C(3)–Mn(1)–Mn(2) = 85.10(5).

2664
S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
carbonyl stretching region similar to those observed for com-
pounds 1–3. The 1H NMR spectrum of 5 displays six well separated
multiplets centered at d 8.04, 7.79, 7.39, 7.11, 6.95 and 6.86 in a
relative intensity of 2:3:10:3:4:4 due to the phenyl and naphthyl
ring protons of the dppn ligand. As expected the 31P{1H} NMR spec-
trum exhibits a singlet a d 49.5. The mass spectrum of 5 exhibits
molecular ion peak at m/z 670 and peaks due to the successive loss
of the carbonyl groups.
the previously reported dinuclear compound [Mn2(CO)8(l-PPh2)2]
4, formed by C–P bond cleavage of the ligand, and the new com-
pound 5, the manganese analog of 3, containing an unaltered che-
lating dppn and a terminal Cl ligand. We have not been able to
isolate any complexes in which the C10 fragment interacts with
metal carbonyl moieties. [Mn2(CO)8(MeCN)2] also reacts with dppn
at room temperature affording compound 6 by a facile cleavage of
one P–C10 bond and the loss of PPh2 group.
Treatment of [Mn2(CO)8(MeCN)2] with a slight excess of dppn in
CH2Cl2, followed by chromatographic separation, lead to the forma-
Supplementary material
tion of compound [Mn2(CO)9{j
1-PPh2(C10H7)}] (6) in 12% yield
(Scheme 3). Compound 6 has been characterized by a combination
of IR, NMR, mass spectral data, elemental analysis and single crystal
X-ray diffraction studies.
CCDC 621647, 672288, 672410, 672289 and 672290 contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
The molecular structure of 6 is shown in Fig. 5 and selected
bond distances and angles are listed in the caption. The molecule
contains a Mn–Mn bond with a length of 2.9124(3) Å, comparable
to that found in [Mn2(CO)10] {2.9030(6) Å} [32]. The overall struc-
ture of 6 is similar to that of [Mn2(CO)10], in which two square-
pyramidal MnL5 groups are joined by a Mn–Mn single bond with
the equatorial ligands adopting a staggered arrangement on the
two metal atoms. The diphenylnaphthylphosphine ligand occupies
one of the axial coordination sites and is formed by the facile P–C
Acknowledgements
We are grateful Prof. Michael Richmond, Department of
Chemistry, University of North Texas, USA, for a generous gift of
the dppn ligand. One of us (F.A.) gratefully acknowledges the
National University of Bangladesh for a study leave.
bond cleavage of the initially coordinated
j
1-dppn ligand and
addition of H at the position vacated by phosphorus. The fate of
this PPh2 fragment remains unknown. Such a facile bond cleavage
was previously observed in the reaction of 1,8-bis(diphenylphos-
phino)naphthalene (dppn) with [Ru3(CO)12] [12]. We were unable
to avoid the ready loss of the PPh2 fragment from dppn, rather than
References
[1] Y. Miyake, Y. Nomaguchi, M. Yuki, Y. Nishibayashi, Organometallics 26 (2007)
3611.
[2] E.L. Diz, A. Neels, H. Stoeckli-Evans, G. Süss-Fink, Polyhedron 20 (2001) 2771.
[3] J.L. Kuiper, P.A. Shapley, C.M. Rayner, Organometallics 23 (2004) 3814.
[4] J.N.L. Dennett, A.L. Gillon, K. Heslop, D.J. Hyett, J.S. Fleming, C.E. Lioyd-Jones,
A.G. Orpen, P.G. Pringle, D.F. Wass, J.N. Scutt, R.H. Weatherhead,
Organometallics 23 (2004) 6078.
[5] I. Albers, J. Alvarez, J. Campora, C.M. Maya, P. Palma, L.J. Sanchez, J. Passaglia, J.
Organomet. Chem. 689 (2004) 833.
[6] A.C. Marr, M. Nieuwenhuyzen, C.L. Pollock, G.C. Saunders, Organometallics 26
(2007) 2659.
[7] T. Costa, H. Schmidbaur, Chem. Ber. 115 (1982) 1374.
[8] R.D. Jackson, S. James, A.G. Orpen, P.G. Pringle, J. Organomet. Chem. 458 (1993)
C4.
[9] (a) E. Drent, P.H.M. Budzelaar, Chem. Soc. Rev. 96 (1996) 663;
(b) A. Abey, G. Consiglio, J. Chem. Soc., Dalton Trans. (1999) 655;
(c) G. Verspui, F. Schanssema, R.A. Sheldon, Angew. Chem. 112 (2000) 825;
G. Verspui, F. Schanssema, R.A. Sheldon, Angew. Chem., Int. Ed. 39 (2000) 804.
and references cited there in;
the further substitution for CO in [Mn2(CO)9{j
1-PPh2(C10H6)PPh2}].
The Mn–P bond length in 6 is 2.2706(4) Å, which is comparable to
the average Mn–P bond distance of 2.23 Å in [Mn2(CO)8(PMePh2)2]
[33]. Most probably, the mono-substituted compound 6 results
from the [Mn2(CO)9(MeCN)] impurity in [Mn2(CO)8(MeCN)2]. We
have demonstrated this by a individual synthesis of 6 from the
room temperature reaction of [Mn2(CO)9(MeCN)] with dppn.
The spectroscopic data for 6 are consistent with the solid-state
structure. The infrared spectrum displays four absorption bands in
the carbonyl stretching region similar to those observed for com-
pounds of the type of ax-[Mn2(CO)9L] [34]. The 1H NMR spectrum
of 6 displays multiplets at d 7.94–7.83 and 7.62–7.42 due to the
phenyl and naphthyl ring protons of the diphenylnaphthylphos-
phine ligand. The mass spectrum of 6 exhibits molecular ion peak
at m/z 674, corresponding to its formulation and ions due to the
successive loss of nine carbonyl groups.
(d) J.K. Hogg, S.L. James, A.G. Orpen, P.G. Pringle, J. Organomet. Chem. 480
(1994) C1;
(e) E. Drent, J.A.M. van Broekhoven, M.J. Doyle, J. Organomet. Chem. 417
(1991) 235;
(f) G.P.C.M. Dekker, C.J. Elsevier, K. Vrieze, P.W.N.M. van Leeuwen,
Organometallics 11 (1992) 1598;
(g) G.P.C.M. Dekker, C.J. Elsevier, K. Vrieze, P.W.N.M. van Leeuwen, C.F.
Roobeek, J. Organomet. Chem. 430 (1992) 357.
[10] M.I. Bruce, P.A. Humphrey, S. Ohucu, R. Schmutzler, B.W. Skelton, A.H. White,
Inorg. Chim. Acta 357 (2004) 1805.
4. Conclusions
[11] M.I. Bruce, P.A. Humphrey, S. Ohucu, R. Schmutzler, B.W. Skelton, A.H. White, J.
Organomet. Chem. 689 (2004) 2415.
[12] M.I. Bruce, P.A. Humphrey, S. Ohucu, R. Schmutzler, B.W. Skelton, A.H. White, J.
Organomet. Chem. 690 (2005) 784.
[13] V.N. Nesterov, W.H. Watson, S. Kandala, M.G. Richmond, Polyhedron 26 (2007)
3602.
[14] W.H. Watson, S. Kandala, M.G. Richmond, J. Organomet. Chem. 692 (2007) 968.
[15] (a) R.D. Jackson, S. James, A.G. Orpen, P.G. Pringle, J. Organomet. Chem. 458
(1993) C3;
(b) A. Karacar, H. Thönnessen, P.G. Jones, R. Bartsch, R. Schmutzler,
Heteroatom. Chem. 8 (1997) 539.
[16] M.I. Bruce, P.J. Jow, J. Organomet. Chem. 519 (1996) 221.
[17] U. Koelle, J. Organomet. Chem. 155 (1978) 53.
[18] SMART Version 5.628, Bruker AXS Inc., Madison, WI, 2003.
[19] SAINT Version 6.36, Bruker AXS Inc., Madison, WI, 2002.
[20] G. Sheldrick, SADABS Version 2.10, University of Göttingen, 2003.
[21] Program XS from SHELXTL Package, V. 6.12, Bruker AXS Inc., Madison, WI, 2001.
[22] Program XL from SHELXTL Package, V. 6.12, Bruker AXS Inc., Madison, WI, 2001.
[23] A.J.C. Wilson (Ed.), International Tables for X-ray Crystallography, vol. C,
Kynoch, Academic Publishers, Dordrecht, 1992. Tables 6.1.1.4 (pp. 500–502)
and 4.2.6.8 (pp. 219–222).
The reactions of the labile complexes [Re2(CO)8(MeCN)2] and
[Mn2(CO)8(MeCN)2] with the diphosphine ligand dppn have been
investigated. This study demonstrates that the reactions of the
sterically demanding dppn ligand with dinuclear rhenium and
manganese carbonyl complexes result mainly in C–H and C–P
bond-cleavage reactions and chelation to one metal center. Three
new mononuclear rhenium complexes bearing terminally coordi-
nated PPh2H and chelating PPh2C10H6 coordinated in the j1
mode (compound 1), cyclometalated (dppndioxide-H) ligand
coordinated in the j1 1-mode (compound 2) and chelating
: -
g1
:
j1
:g
dppn (compound 3) derived from the reaction of [Re2(CO)8-
(MeCN)2] with dppn have been structurally characterized. The
PPh2C10H6 ligand results from cleavage of one P–C10 bond of dppn
with loss of a PPh2 group, which combines with the H of the oxida-
tively added dppn-dioxide ligand in 2 and forms the terminally
coordinated PPh2H in 1. These results contrast with those obtained
from the similar reaction with [Mn2(CO)8(MeCN)2], which afforded
[24] S.E. Kabir, F. Ahmed, A. Das, M.R. Hassan, D.T. Haworth, S.V. Lindeman, T.A.
Siddiquee, D.W. Bennett, J. Organomet. Chem. 693 (2008) 1696.

S.E. Kabir et al. / Journal of Organometallic Chemistry 693 (2008) 2657–2665
2665
[25] S.E. Kabir, F. Ahmed, A. Das, M.R. Hassan, D.T. Haworth, S.V. Lindeman, G.M.G.
Hossain, T.A. Siddiquee, D.W. Bennett, J. Organomet. Chem. 692 (2007)
4337.
[26] (a) T. Scheiring, W. Kaim, J. Fiedler, J. Organomet. Chem. 598 (2000) 136;
(b) W.A. Hermann, P. Kiprof, K. Rypdal, J. Tremmel, R. Blom, R. Alberto, J.
Behm, R.W. Albach, H. Bock, J. Am. Chem. Soc. 113 (1991) 6527.
[27] D.W. Prest, M.J. Mays, P.R. Raithby, A.G. Orpen, J. Chem. Soc., Dalton Trans.
(1982) 737.
[30] A. Karaçar, M. Freytag, H. Thönnessen, J. Omelanczuk, P.G. Jones, R. Bartsch, R.
Schmutzler, Z. Anorg. Allg. Chem. 626 (2000) 2361.
[31] (a) R.G. Hayter, J. Am. Chem. Soc. 86 (1964) 823;
(b) H. Masuda, T. Taga, K. Machida, T. Kawamura, J. Organomet. Chem. 331
(1987) 239.
[32] M.R. Churchill, K.N. Amoh, H.J. Wassermann, Inorg. Chem. 20 (1981) 1609.
[33] M. Laing, T. Ashworth, P. Sommerville, E. Singeton, R. Reimann, J. Chem. Soc.,
Chem. Commun. (1972) 1251.
[28] A.E. Leins, N.J. Coville, J. Organomet. Chem. 464 (1994) 183.
[29] (a) R.D. Adams, L. Chen, W. Wu, Organometallics 12 (1993) 1257;
(b) R.D. Adams, L. Chen, Organometallics 13 (1994) 1264.
[34] (a) R.H. Reimann, E. Singleton, J. Chem. Soc., Dalton Trans. (1976)
2109;
(b) C.C. Grimm, P.E. Brotman, R.J. Clark, Organometallics 9 (1990) 1119.