Reactions of [(CO)3(P-P)Mn]2 with primary alcohols, where, P-P is dppe {Ph2P(CH2)2PPh2}, dppp {Ph2P(CH2)3PPh2}, dppb {Ph2P(CH2)4PPh2}, dpppe {Ph2P(CH2)5PPh2}, dtpe {(p-tol)2P(CH2)

Article abstract of DOI:10.1016/S0022-328X(00)00473-3

Treatment of the manganese(tricarbonyl)diphosphine dimers [(CO)₃(P-P)Mn]₂ (where, P-P is dppe {Ph₂P(CH₂)₂PPh₂}, dppp {Ph₂P(CH₂)₃PPh₂}, dppb {Ph₂P(CH₂)₄PPh₂}, dpppe {Ph₂P(CH₂)₅PPh₂}, dtpe {(p-tol)₂P(CH₂)₂P(p-tol)₂}, and dcpe {(^chex)₂P(CH₂)₂P( ^chex)₂}), with 1-propanol, 1-butanol, 1-pentanol, or 1-hexanol yielded fac-(CO)₃(dppe)MnH (1), fac-(CO)₃(dppp)MnH (2), fac-(CO)₃(dppb)MnH (3), fac-(CO)₃(dpppe)MnH (4), fac-(CO)₃(dtpe)MnH (5), and fac-(CO)₃(dcpe)MnH (6), respectively, and the corresponding aldehydes. Also treatment of Mn₂(CO)₁₀ with P-P in 1-propanol, 1-butanol, 1-pentanol, or 1-hexanol yielded the corresponding manganese(I) hydrides (1-6) and aldehydes. Structural characterization of 5 demonstrates a manganese-hydrogen (Mn-H(1)) bond length of 1.57(3) ? which is in close agreement with the manganese-hydrogen bond length of 1.60(2) ? observed in (CO)₅MnH by neutron diffraction analysis.

Full text of DOI:10.1016/S0022-328X(00)00473-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 613 (2000) 13–18
Reactions of [(CO)3(P-P)Mn]2 with primary alcohols, where, P-P is
dppe {Ph2P(CH2)2PPh2}, dppp {Ph2P(CH2)3PPh2}, dppb
{Ph2P(CH2)4PPh2}, dpppe {Ph2P(CH2)5PPh2}, dtpe
{(p-tol)2P(CH2)2P(p-tol)2}, or dcpe {(chex)2P(CH2)2P(chex)2}.
Synthesis of fac-(CO)3(P-P)MnH and the X-ray structure of
fac-(CO)3(dtpe)MnH
LaKeisha S. O’keiffe a, Alisha C. Mitchell a, Thomas M. Becker b, Douglas M. Ho c,
Santosh K. Mandal a,*
a Department of Chemistry, Morgan State Uni6ersity, Baltimore, MD 21234, USA
b Department of Chemistry, Uni6ersity of Cincinnati, Cincinnati, OH 45221, USA
c Department of Chemistry, Princeton Uni6ersity, Princeton, NJ 08544, USA
Received 28 March 2000; received in revised form 16 May 2000
Abstract
Treatment of the manganese(tricarbonyl)diphosphine dimers [(CO)3(P-P)Mn]2 (where, P-P is dppe {Ph2P(CH2)2PPh2}, dppp
{Ph2P(CH2)3PPh2}, dppb {Ph2P(CH2)4PPh2}, dpppe {Ph2P(CH2)5PPh2}, dtpe {(p-tol)2P(CH2)2P(p-tol)2}, and dcpe
{(chex)2P(CH2)2P(chex)2}), with 1-propanol, 1-butanol, 1-pentanol, or 1-hexanol yielded fac-(CO)3(dppe)MnH (1), fac-
(CO)3(dppp)MnH (2), fac-(CO)3(dppb)MnH (3), fac-(CO)3(dpppe)MnH (4), fac-(CO)3(dtpe)MnH (5), and fac-(CO)3(dcpe)MnH
(6), respectively, and the corresponding aldehydes. Also treatment of Mn2(CO)10 with P-P in 1-propanol, 1-butanol, 1-pentanol,
or 1-hexanol yielded the corresponding manganese(I) hydrides (1–6) and aldehydes. Structural characterization of 5 demonstrates
,
a manganese–hydrogen (Mn–H(1)) bond length of 1.57(3) A which is in close agreement with the manganese–hydrogen bond
,
length of 1.60(2) A observed in (CO)5MnH by neutron diffraction analysis. © 2000 Elsevier Science B.V. All rights reserved.
Keywords: Manganese; Diphosphines; Dimers; Hydrides; X-ray
product of the alcohol [3]. However, no detailed studies
of the reactions of isolated manganese(tricarbonyl)-
diphosphine dimers, [(CO)3(P-P)Mn]2 with alcohols
have been reported. Also it is not known whether the
reactions of [(CO)3(P-P)Mn]2 with alcohols produce the
corresponding aldehydes. In this paper we present re-
sults of the reactions of [(CO)3(P-P)Mn]2 (where P-P is
dppe, dppp, dppb {Ph2P(CH2)4PPh2}, dpppe
{Ph2P(CH2)5PPh2}, dtpe {(p-tol)2P(CH2)2P(p-tol)2},
and dcpe {(chex)2P(CH2)2P(chex)2}), with 1-propanol,
1-butanol, 1-pentanol and 1-hexanol. Also presented
are the direct and convenient syntheses of the mangane-
se(I) hydrides, fac-(CO)3(dppe)MnH (1), fac-(CO)3-
(dppp)MnH (2), fac-(CO)3(dppb)MnH (3), fac-
(CO)3(dpppe)MnH (4), fac-(CO)3(dtpe)MnH (5), and
1. Introduction
Reactions of Mn2(CO)10 with dppe {Ph2P(CH2)2-
PPh2} and dppp {Ph2P(CH2)3PPh2} in 1-propanol [1,2]
or 1-pentanol [3] and dppfe {1,1%-bis(diphenylphos-
phino)ferrocene} in 1-propanol [4] have been reported
to yield the corresponding tricarbonyl(diphosphine)
-manganese hydrides, fac-(CO)3(P-P)MnH in 2–11 h. It
has been reported that [(CO)3(dppe)Mn]2 and [(CO)3-
(dppp)Mn]2 are the intermediates in the reactions of
Mn2(CO)10 with dppe and Mn2(CO)10 with dppp re-
spectively in 1-pentanol and pentanal is the oxidation
* Corresponding author. Fax: +1-410-319-3778.
E-mail address: smandal@morgan.edu (S.K. Mandal).
0022-328X/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00473-3

14
L.S. O’keiffe et al. / Journal of Organometallic Chemistry 613 (2000) 13–18
fac-(CO)3(dcpe)MnH (6), from the reactions of
Mn2(CO)10 with the corresponding diphosphines (P-P)
in 1-propanol, 1-butanol, 1- pentanol, and 1-hexanol
and the X-ray crystal structure of 5.
structures (P-P)(CO)3Mn–Mn(CO)3(P-P), with one
diphosphine ligand bonded to each metal atom, were
proposed for the dimers [(CO)3(dppm)Mn]2 and
[(CO)3(dppe)Mn]2 [5]. We believe that the dppp, dpppe,
dcpe and dtpe dimers have similar symmetrical
structures.
2. Results and discussion
2.2. Reactions of [(CO)3(P-P)Mn]2, with 1-propanol,
1-butanol, 1-pentanol or 1-hexanol and spectral studies
of the hydrides 1–6
2.1. Synthesis and characterizations of the manganese
diphosphine dimers [(CO)3(P-P)Mn]2
Treatment of [(CO)3(P-P)Mn]2 with 1-propanol, 1-
butanol, 1-pentanol or 1-hexanol yielded the corre-
sponding hydrides fac-(CO)3(P-P)MnH (1–6) and
aldehydes. For example, fac-(CO)3(dppb)MnH (3) was
prepared by allowing [(CO)3(dppb)Mn]2 to react with
boiling 1-propanol, Eq. (2):
The diphosphine dimers [(CO)3(dppm)Mn]2 and
[(CO)3(dppe)Mn]2, where dppm=bis(diphenylphos-
phino)methane, were synthesized previously from the
reaction of Mn2(CO)10 with the corresponding diphos-
phines in boiling benzene [5] according to Eq. (1).
Mn2(CO)10+P-P“[(CO)3(P-P)Mn]2+4CO
(1)
[(CO)3(dppb)Mn]2+CH3CH2CH2OH
The diphosphine dimers [(CO)3(dppp)Mn]2,
“2fac-(CO)3(dppb)MnH, 3+CH3CH2CHO
(2)
[(CO)3(dppb)Mn]2, [(CO)3(dpppe)Mn]2, [(CO)3(dtpe)-
Mn]2, and [(CO)3(dcpe)Mn]2 were synthesized using the
procedure noted above [5]. The yields of the dimers
range from 34–41%. Attempts to synthesize the diphos-
phine dimer, [(CO)3(dpph)Mn]2, where dpph is 1,6-bis-
(diphenylphosphino)hexane, were unsuccessful. The
diphosphine dimers are extremely air sensitve as re-
ported previously [5]. We have observed that the
diphosphine dimers spontaneously decarbonylate to
unidentified compounds at room temperature. There-
fore, these compounds were stored in sample tubes
filled with CO at −25°C. Our attempts to replace
benzene with toluene did not yield any diphosphine
dimers. Instead, the corresponding hydrides, fac-
(CO)3(P-P)MnH were obtained. Toluene, xylene and
tetrahydrofuran have been used as the solvents as well
as the hydrogen source for the preparation of many
hydrides [6–8]. For example, the hydride (CO)3[h5-
C5H4PPh2)(h7-C7H6PPh2)Ti]MnH was synthesized
from the reaction of Mn2(CO)10 with two equivalents of
[h5-C5H4PPh2)(h7-C7H6PPh2)Ti] in boiling toluene [6].
The dimers [(CO)3(P-P)Mn]2 were characterized by
IR spectroscopy only. The IR spectrum of each diphos-
phine dimer exhibits two w(CꢀO) in the region 1900–
1850 cm−1 which was previously observed in the IR
spectrum of [(CO)3(dppm)Mn]2 and [(CO)3(dppe)Mn]2
[5]. The intensity of the high frequency band is about
two times higher than the intensity of the low frequency
Almost quantitative yields of 1–6 were obtained in
0.5–3 h. The times required for the complete conver-
sion of the diphosphine dimers to the corresponding
hydrides were less in higher boiling alcohols. For exam-
ple, all diphosphine dimers were converted completely
to the corresponding hydrides in 0.5–0.75 h in 1-hex-
anol. The hydrides were separated by filtration. A small
amount of the corresponding aldehydes was extracted
in CH2Cl2 by solvent extraction of the filtrate with 1:2
CH2Cl2–water.
The hydrides 1 and 2 were characterized previously
[1,2]. The IR spectral data for the complexes 3–6 are
given in Section 3. The IR spectrum of each of the
compounds 3–6 shows three strong w(CꢁO) expected
1
for facial geometry of the terminal carbonyls. The H
and 13C-NMR spectral data are given in Section 3. As
1
expected, the H-NMR spectral data of each of com-
pounds 3–6 exhibit one triplet for the hydride proton
coupled to phosphorus. Similar triplets for the hydride
1
protons were also observed in the H spectra of 1 [9], 2
[2], fac-(CO)3(dppe)ReH [10], and fac-(CO)3(dppp)ReH
[11]. The 13C-NMR spectrum of each of compounds
3–6 exhibits two triplets for the two sets of terminal
carbonyls as was observed in the corresponding formyl
and methoxymethyl complexes [12].
We did not study the mechanism of the reactions of
the diphosphine dimers with alcohols. However, we
recently observed that the reaction of one equivalent of
Re2(CO)10 with two equivalents of dppp in the presence
of CO2 in boiling pentanol/propanol yielded one equiv-
alent of fac-(CO)3(dppp)ReH and one equivalent of
propyl carbonato complex, fac-(CO)3(dppp)ReOC(O)-
OCH2CH2CH3 [13]. The carbonato complex is formed
presumably from the reaction of CO2 with the interme-
diate alkoxide, (CO)3(dppp)ReOCH2CH2CH3. The
above reaction did not yield any carbonato complex in
1
band. The H-NMR spectra are not helpful because no
functional groups are present in the dimers. We knew
that 13C-NMR spectra would be helpful. Unfortu-
nately, the diphosphine dimers did not survive in
CH2Cl2 over a period of 1–2 h at ambient temperature.
Low temperature studies were not performed because
13C-NMR spectra of many manganese carbonyl com-
plexes exhibited a very low intensity broad signal due to
carbonyl carbon resonances [2]. Symmetrical dimeric

L.S. O’keiffe et al. / Journal of Organometallic Chemistry 613 (2000) 13–18
15
the absence of CO2; only two equivalents of the hy-
Mn2(CO)10+2dppb+CH3CH2CH2OH
dride, fac-(CO)3(dppp)ReH were obtained. However,
the reaction of the manganese diphosphine dimers in
the presence of CO2 in boiling alcohols yielded only the
corresponding hydrides; carbonato complexes were not
obtained. We believe that the diphosphine dimers,
[(CO)3(P-P)Mn]2 react with alcohols to yield one equiv-
alent of the corresponding hydrides, fac-(CO)3(P-
P)MnH and one equivalent of the intermediate
alkoxides, fac-(CO)3(P-P)MnOCH2R which b-eliminate
the corresponding hydrides, fac-(CO)3(P-P)MnH and
aldehydes, RCHO, as shown in Eq. (3).
“2fac-(CO)3(dppb)MnH, 1+CH3CH2CHO
(4)
When the reactions were complete, as indicated by
the IR spectra of the reaction mixtures, the correspond-
ing hydrides were separated from the mother liquors.
The yields of the hydrides 1–6 were 60–90% in various
alcohols. The aldehydes were separated according to
the methods described in Section 2.2. Attempts to
synthesize the hydride fac-(CO)3(dpph)MnH were
unsuccessful.
2.4. X-ray structure of 5
Mn2(CO)10+P-P“(P-P)(CO)3MnꢂMn(CO)3(P-P)
The conformation and atomic numbering scheme for
5 are shown in Fig. 1. Crystal data for 5 were obtained
under the conditions summarized in Table 1. The se-
lected bond lengths and angles for 5 are compiled in
Table 2. The Mn atom in 5 is octahedrally coordinated
to three carbonyls, dtpe {(p-tol)2P(CH2)2P(p-tol)2}, and
the hydride. The observed Mn–H(1) bond length of
(P-P)(CO)3MnꢂMn(CO)3(P-P)+RCH2OH
“(P-P)(CO)3MnH+RCH2OMn(CO)3(P-P)
(P-P)(CO)3MnOCH2R“(P-P)(CO)3MnH+RCHO
(3)
,
1.57(3) A is in excellent agreement with the (CO)5Mn–
2.3. Direct synthesis of the hydrides
fac-(CO)3(P-P)MnH (1–6)
,
H bond length of 1.60(2) A determined by neutron
diffraction [14]. The P(1)–Mn–P(2) angle of 85.08(2)°
is lower than the corresponding P(1)–Mn–P(2) angle of
95.83(5)° observed in fac-(CO)3(dppfe)MnH [4] and
similar to the corresponding P(1)–Mn–P(2) angles of
84.81(3)° in fac-(CO)3(depe)MnCl [15], 84.4(1)° in fac-
(CO)3(dppe)MnNCO [16], and 84.6(1)° in fac-
(CO)3(dppe)MnOC(O)OCH3 [2]. The average Mn–P
bond length of 2.263(7) A is almost equal to the
corresponding Mn–P bond lengths of 2.267(2) A in
mer, trans-(CO)3{P(C6H5)3}2MnH [17] and 2.255(2) A
in mer, trans-(CO)3{P(CH3)(C6H5)2}2MnH [18].
Syntheses of the hydrides 1 and 2 in 1-propanol and
1-pentanol have been reported previously [1–3]. The
hydrides 1 and 2 have been prepared by us also in
1-butanol and 1-hexanol. The hydrides 3–6 have been
synthesized in 1-propanol, 1-butanol, 1-pentanol and
1-hexanol using the same procedures. For example, the
hydride fac-(CO)3(dppb)MnH (3) was prepared from
the reaction of dppb with Mn2(CO)10 in boiling 1-
propanol, Eq. (4):
,
,
,
Fig. 1. A perspective drawing of molecule 5.

16
L.S. O’keiffe et al. / Journal of Organometallic Chemistry 613 (2000) 13–18
Table 1
Summary of crystal data for fac-(CO)3(dtpe)MnH (5)
Color and habit
Pale yellow plate
Scan mode
ꢀ, 1°×530
Crystal size (mm)
Unit cell parameters
0.12×0.24×0.25
Limiting indices
Chemical formula
Absorption correction
Reflections collected
Reflections/Rint
Reflections observed
No. of variables
R/wR2 [I\2|(I)] a
Goodness-of-fit
05h519, 05k515, −275l525
C33H33MnO3P2
Gaussian
33411
8123 (0.0636)
6088
360
0.0392/0.0790
,
a (A)
14.0352(4)
10.8625(3)
19.6268(6)
2992.2(2)
,
b (A)
,
c (A)
3
,
V (A )
,
Wavelength (A)
Crystal system
Space group
Z
0.71073
Orthorhombic
Pna2(1) (no. 33)
4
1.014
Refinement method
Full-matrix least-squares on F2
Diffractometer
v(Mo–Ka) (mm−1
q range (°)
Nonius Kappa CCD
0.580
2.08–30.02
)
a Definitions of R and wR2: R=(ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ)/ꢀꢁFoꢁ; wR2=[ꢀwi(ꢁFoꢁ −ꢁFcꢁ ) /ꢀwiꢁF2oꢁ2]1/2
.
2
2 2
3. Experimental
Elemental analyses were not performed because the
dimers were not stable at room temperature.
All manipulations were carried out under an argon
atmosphere and the solvents were dried prior to use.
Reagent grade chemicals were used without further
purification. Mn2(CO)10, dppe, dppp, dpppe, dtpe, and
dcpe were obtained from commercial sources.
3.2. Reactions of [(CO)3(P-P)Mn]2, with 1-propanol,
1-butanol, 1-pentanol or 1-hexanol and spectral studies
of the hydrides 1–6
IR spectra were recorded on a Perkin–Elmer 1600
series FT-IR instrument. NMR spectra were recorded
To 25 ml of primary alcohol (1-propanol, 1-butanol,
1-pentanol or 1-hexanol) was added 0.84–0.93 mmol of
the dimers [(CO)3(P-P)Mn]2. The slurries were heated at
the boiling point of the alcohols. The reactions were
1
on a Bruker AC 250 (250.133 MHz, H; 62.896 MHz,
13C) spectrometer. Melting points were recorded on a
Mel-Temp apparatus and are uncorrected. Microanaly-
ses were conducted by Quantitative Technologies Inc.
Table 2
,
Selected bond lengths (A) and angles (°) for fac-Mn(CO)3(dtpe)H (5)
3.1. Synthesis and characterization of the manganese
diphosphine dimers [(CO)3(P-P)Mn]2
Mn–C(3)
Mn–C(2)
Mn–C(1)
Mn–P(1)
Mn–P(2)
Mn–H(1)
C(1)–O(1)
C(2)–O(2)
1.801(2)
1.803(3)
1.812(3)
2.2612(7)
2.2645(7)
1.57(3)
C(3)–O(3)
P(1)–C(6)
P(1)–C(13)
P(1)–C(4)
C(4)–C(5)
P(2)–C(5)
P(2)–C(20)
P(2)–C(27)
1.150(3)
1.822(2)
1.834(2)
1.835(2)
1.532(3)
1.852(2)
1.827(2)
1.828(2)
To 25 ml of benzene were added 2.56 mmol of
Mn2(CO)10 and 5.12 mmol of diphosphines (dppp,
dppb, dpppe, dtpe or dcpe). The benzene solutions were
refluxed under argon and the reactions were monitored
with IR. The reflux times required for complete conver-
sion of Mn2(CO)10 to the dimers, [(CO)3(P-P)Mn]2 were
4–6 h. The resultant solutions were allowed to cool to
room temperature. Air-sensitive, yellow crystalline
dimers were collected by filtration. The crystals were
washed with hexane and stored at −35°C in glass
tubes filled with CO. The yields of the dimers were
34–41%. Data for [(CO)3(dppp)Mn]2: m.p. 202–205°C
with decomposition. IR (cm−1, CH2Cl2): w(CꢁO) 1897s
and 1859m. Data for [(CO)3(dppb)Mn]2: m.p. 167–
170°C with decomposition. IR (cm−1, CH2Cl2): w(CꢁO)
1896s and 1857m. Data for [(CO)3(dpppe)Mn]2: m.p.
180–185°C with decomposition. IR (cm−1, CH2Cl2):
w(CꢁO) 1897s and 1859m. Data for [(CO)3(dtpe)Mn]2:
1.144(3)
1.140(3)
C(3)–Mn–C(2)
C(3)–Mn–C(1)
C(2)–Mn–C(1)
C(3)–Mn–P(1)
C(2)–Mn–P(1)
C(1)–Mn–P(1)
C(3)–Mn–P(2)
C(2)–Mn–P(2)
C(1)–Mn–P(2)
P(1)–Mn–P(2)
C(3)–Mn–H(1)
C(2)–Mn–H(1)
C(1)–Mn–H(1)
P(1)–Mn–H(1)
P(2)–Mn–H(1)
O(1)–C(1)–Mn
O(2)–C(2)–Mn
O(3)–C(3)–Mn
93.17(12)
98.56(11)
96.54(13)
88.89(8)
167.61(11)
95.23(8)
167.61(8)
90.49(9)
92.76(7)
85.08(2)
83.1(12)
86.7(12)
176.3(12)
81.5(12)
85.3(12)
179.4(2)
178.3(3)
176.3(2)
C(6)–P(1)–C(4)
C(13)–P(1)–C(4)
C(6)–P(1)–Mn
C(13)–P(1)–Mn
C(4)–P(1)–Mn
C(5)–C(4)–P(1)
C(4)–C(5)–P(2)
106.50(11)
104.77(10)
116.80(7)
118.83(7)
108.19(8)
108.7(2)
107.67(14)
C(20)–P(2)–C(27) 102.57(11)
C(20)–P(2)–C(5)
C(27)–P(2)–C(5)
C(20)–P(2)–Mn
C(27)–P(2)–Mn
C(5)–P(2)–Mn
C(7)–C(6)–P(1)
C(11)–C(6)–P(1)
C(25)–C(20)–P(2) 119.6(2)
C(21)–C(20)–P(2) 121.8(2)
C(28)–C(27)–P(2) 121.5(2)
C(32)–C(27)–P(2) 120.9(2)
106.08(10)
103.05(12)
114.62(8)
120.08(8)
109.06(8)
125.3(2)
116.0(2)
m.p. 150–155°C with decomposition. IR (cm−1
CH2Cl2): w(CꢁO) 1900s and 1862m. Data for
[(CO)3(dcpe)Mn]2: m.p. 138–143°C with decomposi-
tion. IR (cm−1, CH2Cl2): w(CꢁO) 1890s and 1850.
,
C(6)–P(1)–C(13) 100.53(10)

L.S. O’keiffe et al. / Journal of Organometallic Chemistry 613 (2000) 13–18
17
into small test tubes and the solvents were removed by
passing a stream of argon through the solutions. The
oily residues in the test tubes were dissolved in CH2Cl2.
The IR spectra of the CH2Cl2 solutions of the oily
residues confirmed the presence of the corresponding
aldehydes and manganese hydrides in the filtrates; the
w(CꢀO) of the aldehydes formed from the oxidation of
the corresponding alcohols match with the w(CꢀO) of
the commercially available aldehydes. For example, the
IR spectra of the CH2Cl2 solutions of propanal, 1-bu-
tanal, 1-pentanal, and 1-hexanal obtained from both
sources exhibit w(CꢀO) at 1732, 1724, 1726, and 1723
cm−1 respectively. Now the rest of the filtrates were
concentrated to about 2–3 ml and then cooled to 0°C.
At this time some solids were separated from the con-
centrated, cooled filtrates. A small amount of the corre-
sponding aldehydes were extracted in CH2Cl2 by
solvent extractions of the filtrates with 15 ml of 1:2
CH2Cl2–water.
monitored with IR. The reflux times required for com-
plete conversion of the dimers to the hydrides 1–6 in
1-propanol were 2.0, 1.5, 2.0, 3.0, 3.0, and 2.5 h respec-
tively. The reflux times required for complete conver-
sion were less in higher boiling alcohols. For example,
the dimers were completely converted to the corre-
sponding hydrides in 0.5–0.75 h using 1-hexanol. When
the reactions were complete, the mixtures were cooled
to 0°C. The hydrides were separated by filtration and
the filtrates, which contain the corresponding alcohols,
oxidized products of the alcohols, and small amounts
of hydrides, were kept aside for further work. The solid
hydrides were washed with the corresponding alcohols
(2×5 ml) and hexane (2×5 ml). The yields of the
hydrides were 95–98%. The hydrides 1 and 2 were
characterized previously. Data for 3: m.p. 202–205°C.
IR (cm−1, CH2Cl2): w(CꢁO) 1995vs, 1916s, and 1900s.
1H-NMR (l, C6D6): 7.35 (m, 20H, C6H5), 2.50 (m, 8H,
CH2CH2CH2CH2), −6.50 (t, J(PH)=45 Hz, H). 13C-
NMR (l, C6D6): 223.4 (t, J(PC)=7 Hz, 2CꢁO), 221.8
(s, br, CꢁO), 140.0–127.6 (m, C6H5), 33.0 (t, J(PC)=
11 Hz, PCH2), 23.5 (s, CH2CH2CH2CH2). Anal.
Found: C, 65.2; H, 5.2. Calc. for C31H29MnO3P2: C,
65.7; H, 5.2%. Data for 4: m.p. 208–210°C with decom-
position. IR (cm−1, CH2Cl2): w(CꢁO) 1995vs, 1915s,
3.3. Direct synthesis of the hydrides
fac-(CO)3(P-P)MnH (1–6)
Mixtures of 2.564 mmol of Mn2(CO)10, 5.128 mmol
of diphosphines (dppb, dpppe, dtpe, or dcpe), and 25
ml of alcohols (1-propanol, 1-butanol, 1-pentanol, or
1-hexanol) and mixtures of 2.564 mmol of Mn2(CO)10,
5.128 mmol of diphosphines (dppe or dppp) and 25 ml
of alcohols (1-butanol or 1-hexanol) were heated to
reflux and the reactions were monitored with IR peri-
odically. The reflux times required for complete conver-
sion of Mn2(CO)10 to the corresponding hydrides 3–6
in 1-propanol were 2.0, 3.0, 3.0, and 2.5 h respectively.
The reflux times required for complete conversion were
less in higher boiling alcohols. For example, the diphos-
phine dimers were completely converted to the corre-
sponding hydrides in 0.5–1.0 h using 1-hexanol. The
reflux times required for complete conversion of
Mn2(CO)10 to the hydrides 1 and 2 were 2.5–3.0 h in
1-butanol and 0.5–0.75 h in 1-hexanol. When the reac-
tions were complete, the mixtures were cooled to 0°C.
The hydrides were separated by filtration and the
filtrates, which contain the corresponding alcohols, oxi-
dized products of the alcohols, and small amount of
hydrides, were kept aside for further work. The solid
hydrides were washed with the corresponding alcohols
(2×5 ml) and hexane (2×5 ml). The yields of the
hydrides were 60–90%. The characterizations of the
hydrides have been reported in Section 3.2. Also the
procedure for the detection of the aldehydes in the
filtrates have been discussed in Section 3.2 above.
1
and 1900s. H-NMR (l, C6D6): 7.38 (m, 20H, C6H5),
2.14–1.33 (m, 10H, CH2CH2CH2CH2CH2), −6.51 (t,
J(PH)=47 Hz, H). 13C-NMR (l, C6D6): 223.5 (t,
J(PC)=8 Hz, 2CꢁO), 221.8 (t, J(PC)=14 Hz, CꢁO),
140.3–129.5 (m, C6H5), 33.0 (t, J(PC)=11 Hz, PCH2),
23.6 (s, CH2CH2CH2CH2CH2). Anal. Found: C, 65.6;
H, 5.2. Calc. for C32H31MnO3P2: C, 66.2; H, 5.3%.
Data for 5: m.p.188–190°C. IR (cm−1, CH2Cl2):
w(CꢁO) 1993vs and 1906vs, br. 1H-NMR (l, C6D6):
7.84–6.89 (m, 16H, –C6H4–), 2.50 (m, 8H,
CH2CH2CH2CH2), 1.98 (s, 12H, CH3), −7.59 (t,
J(PH)=47 Hz, H). 13C-NMR (l, C6D6): 225.5 (t,
J(PC)=6 Hz, 2CꢁO), 221.8 (t, J(PC)=12 Hz, CꢁO),
140.1/139.9 (s, p, C6H5), 134.9–134.08 (m, ipso, C6H5),
133.2/131.6 (t, J(PC)=5/5 Hz, o, C6H5), 129.6/129 (t,
J(PC)=5/5 Hz, m, C6H5), 29.9 (t, J(PC)=22 Hz,
PCH2), 21.1 (s, CH3). Anal. Found: C, 66.4; H, 5.7.
Calc. for C33H33MnO3P2: C, 66.7; H, 5.6%. Data for 6:
m.p. 161–163°C. IR (cm−1
,
toluene): w(CꢁO)
1985vs, 1907s, and 1888s. 1H-NMR (l, C6D6): 2.36
(s, br, 4 H, –PCH2CH2P–), 1.87–0.97 (m, 44 H,
–CHCH2CH2CH2CH2CH2), −8.87 (t, J(PH)=48 Hz,
H)». ¹¹¹¹¹¹¹¹¹¹¹¼
13C-NMR (l, C6D6): 226.1 (t, J(PC)=5 Hz,
2CꢁO), 223.9 (s, br, CꢁO), 40.0–26.3 (m, –C6H11), 23.8
(t, J(PC)=19 Hz, PCH2). Anal. Found: C, 60.9; H,
8.8. Calc. for C29H49MnO3P2: C, 61.8; H, 8.8%.
3.4. X-ray crystal structure of fac-(CO)3(dtpe)MnH (5)
About 0.5 ml of the filtrates, which contain the
corresponding alcohols, oxidized products of the alco-
hols, and small amount of hydrides, were transferred
Crystals of 5 were grown from CH2Cl2–hexane at
−5°C. Data were collected on a Nonius KappaCCD

18
L.S. O’keiffe et al. / Journal of Organometallic Chemistry 613 (2000) 13–18
diffractometer and corrected for Lorentz-polarization
and absorption effects. The structure was solved by
direct methods and refined by full-matrix least-squares
on F2 using SHELXTL (version 5). The non-hydrogen
atoms were refined anisotropically and the hydrogens
were assigned isotropic displacement coefficients
U(H)=1.2U(C) or 1.5U(Cmethyl) and allowed to ride
on their respective carbons. The hydride atom H(1) was
located in a difference-Fourier map, and its coordinates
and isotropic displacement coefficient were free to vary.
Convergence gave R=0.0392 for 6088 reflections with
F]4|(F). Additional crystallographic data and results
are summarized in Tables 1 and 2.
References
[1] B.D. Dombek, Ann. N.Y. Acad. Sci. 415 (1983) 176.
[2] S.K. Mandal, D.M. Ho, M. Orchin, Organometallics 12 (1993)
1724.
[3] S.K. Mandal, J. Feldman, M. Orchin, J. Coord. Chem. 33 (1994)
219.
[4] S. Onaka, M. Haga, S. Takagi, M. Otsuka, K. Mizuno, Bull.
Chem. Soc. Jpn. 67 (1994) 2440.
[5] R.H. Reimann, E. Singleton, J. Organomet. Chem. 38 (1972) 113.
[6] M.D. Rausch, M. Ogasa, M.A. Ayers, R.D. Rogers, A.N. Rollins,
Organometallics 10 (1991) 2481.
[7] R. Ugo, F. Bonati, J. Organomet. Chem. 8 (1967) 189.
[8] P.Y. Zheng, D.W. Stephan, Can. J. Chem. 67 (1989) 1584.
[9] B.L. Booth, R.N. Haszeldine, J. Chem. Soc. A (1966) 157.
[10] N. Flitcroft, J.M. Leach, F.J. Hopton, J. Inorg. Nucl. Chem. 32
(1970) 137.
[11] S.K. Mandal, D.M. Ho, M. Orchin, J. Organomet. Chem. 439
(1992) 53.
[12] S.K. Mandal, J.A. Krause, M. Orchin, J. Organomet. Chem. 467
(1994) 113.
4. Supplementary material
[13] The molecular structure of the propyl carbonato complex, fac-
(CO)3(dppp)ReOC(O)OCH2CH2CH3 has been confirmed by X-
ray crystal structure determination (unpublished results).
[14] S.J. La Placa, W.C. Hamilton, J.A. Ibers, A. Davidson, Inorg.
Chem. 8 (1969) 1928.
[15] G.Q. Li, R.M. Burns, S.K. Mandal, J.K. Bauer, M. Orchin, J.
Organomet. Chem. 549 (1997) 89.
[16] S.K. Mandal, D.M. Ho, M. Orchin, Polyhedron 11 (1992) 2055.
[17] H. Hayakawa, H. Nakayama, A. Kobayashi, Y. Sasaki, Bull.
Chem. Soc. Jpn. 51 (1978) 2041.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 138490 for compound 5.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (Fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
[18] M. Laing, E. Singleton, G. Kruger, J. Organomet. Chem. 54 (1973)
C30.
.