Reactions of dirhenium heptoxide with manganese(I) and rhenium(I) hydrido alkoxo, methylcarbonato, carbonato-bridged, and methoxymethyl complexes. The X-ray structures of fac-(CO)3(dppp)MnOReO3 and fac-(CO)3(dppp)ReOReO<su

Article abstract of DOI:10.1016/S0022-328X(02)01632-7

Treatment of Re₂O₇ with manganese(I) and rhenium(I) hydrido {fac-(CO)₃(P-P)MH}, alkoxo {fac-(CO)₃(P-P)MOR}, methylcarbonato {fac-(CO)₃(P-P)MOC(O)OCH₃}, carbonato-bridged [(CO)₃(P

Full text of DOI:10.1016/S0022-328X(02)01632-7

Journal of Organometallic Chemistry 658 (2002) 88Á93
/
www.elsevier.com/locate/jorganchem
Reactions of dirhenium heptoxide with manganese(I) and rhenium(I)
hydrido, alkoxo, methylcarbonato, carbonato-bridged, and
methoxymethyl complexes. The X-ray structures of fac-
(CO)3(dppp)MnOReO3 and fac-(CO)3(dppp)ReOReO3
Damon A. Brown a, David M. Kimari a, Anna M. Duzs-Moore a, Theodore
A. Budzichowski b, Douglas M. Ho c, Santosh K. Mandal a,*
a Department of Chemistry, Morgan State University, Baltimore, MD 21251, USA
b Department of Chemistry, University of Maryland Baltimore County, Baltimore, MD 21250, USA
c Department of Chemistry, Princeton University, Princeton, NJ 08544, USA
Received 11 January 2002; received in revised form 31 May 2002; accepted 31 May 2002
Abstract
Treatment of Re2O7 with manganese(I) and rhenium(I) hydrido {fac-(CO)3(Pꢀ
methylcarbonato {fac-(CO)3(PꢀP)MOC(O)OCH3}, carbonato-bridged [(CO)3(PꢀP)M]2{m-OC(O)O} and methoxymethyl {fac-
(CO)3(PꢀP)MCH2OCH3} complexes, where, R is CH3 or CH2CH3, PꢀP is dppe {1,2-bis(diphenylphosphino)ethane} or dppp {1,3-
bis(diphenylphosphino)propane}, yielded the corresponding perrhenato complexes, fac-(CO)3(PꢀP)MOReO3 (1, MꢀMn, PꢀPꢀ
dppe; 2, MꢀMn, PꢀPꢀdppp; 3, MꢀRe, PꢀPꢀdppe; 4, MꢀRe, PꢀPꢀdppp), in moderate to excellent yield. The perrhenato
/
P)MH}, alkoxo {fac-(CO)3(Pꢀ/P)MOR},
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
complexes have been characterized spectroscopically and the molecular structures of fac-(CO)3(dppp)MnOReO3, 2 and fac-
(CO)3(dppp)ReOReO3, 4 have been established through X-ray crystallography. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Manganese; Rhenium; Rhenium heptoxide; Perrhenato complexes; X-ray
1. Introduction
P)MOR},
C(O)OCH3}, carbonato-bridged [(CO)3(Pꢀ
OC(O)O}, and methoxymethyl
{fac-(CO)3(Pꢀ
P)MCH2OCH3} complexes, where, R is CH3 or
CH2CH3 and PꢀP is 1,2-bis(diphenylphosphino)ethane
(dppe) or 1,3-bis(diphenylphosphino)propane (dppp)
and the X-ray structures of fac-(CO)3(dppp)MnOReO3,
2 and fac-(CO)3(dppp)ReOReO3, 4.
methylcarbonato
{fac-(CO)3(Pꢀ
/
P)MO-
/
P)M]2{m-
Dirhenium heptoxide was used extensively for the
synthesis of numerous alkyl and arylrhenium oxides and
related complexes [1]. Treatments of silanols with Re2O7
were reported to yield the corresponding siloxane
perrhenates [2]. We have observed that Re2O7 reacts
with a variety of metal carbonyl complexes to afford the
corresponding metal carbonyl perrhenato complexes [3].
However, analogous perrhenato complexes were synthe-
sized previously from the reaction of the corresponding
metal carbonyl halides with AgReO4. For example,
(CO)5ReOReO3 was synthesized from the reaction of
(CO)5ReCl with AgReO4 [4]. Here we present the
reactions of Re2O7 with manganese(I) and rhenium(I)
/
/
2. Results and discussion
2.1. Reactions of hydrido manganese(I) and rhenium(I)
complexes, fac-(CO)3(Pꢀ/P)MH with Re2O7
hydrido {fac-(CO)3(Pꢀ
/
P)MH}, alkoxo {fac-(CO)3(Pꢀ
/
The reaction of fac-(CO)3(Pꢀ
/
P)MH with Re2O7 (2:1
mol ratio) in moist dichloromethane yielded the corre-
sponding
perrhenato
complexes,
4, in high yield (Eq. (1)):
fac-(CO)3(Pꢀ
/
* Corresponding author
E-mail address: smandal@morgan.edu (S.K. Mandal).
P)MOReO3, 1Á
/
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 1 6 3 2 - 7

D.A. Brown et al. / Journal of Organometallic Chemistry 658 (2002) 88Á
/93
89
2fac(CO)3(PꢀP)MHꢁRe2O7 ꢁH2O
0 2fac(CO)3(PꢀP)MOReO3; 1Á4ꢁ2H2
yield (Eq. (3)):
(CO)3(PꢀP)MOC(O)OCH3 ꢁRe2O7
(1)
Similar synthesis of the platinum perrhenato complex,
[Pt4(m-CO)2(PPh3)4(ReO4)2], from the reaction of the
platinum hydrido complex, [Pt4H(CO)(m-CO)3(P-
Ph3)4]ReO4, with Re2O7 in moist dichloromethane was
0 fac(CO)3(PꢀP)MOReO3 ꢁCH3OReO3 ꢁCO2 (3)
The black precipitates are presumed to be lower
oxides of rhenium.
reported previously [5]. The perrhenato complexes, 1Á
were characterized spectroscopically. The IR spectrum
of each exhibits three strong n(CꢁO)’s characteristic of
facial geometry. Two medium intensity bands in the
region 955Á
900 cmꢂ1 are attributed to the ReO
/
4,
2.4. Reactions of carbonato-bridged complexes,
/
[(CO)3(Pꢀ/P)M]2{m-OC(O)O} with Re2O7
/
When an equimolar mixture of [(CO)3(Pꢀ
/
P)M]2{m-
vibrations of the perrhenates. Similar bands were also
1
observed in related perrhenato complexes [4]. The H-
OC(O)O} and Re2O7 in dichloromethane was stirred,
the corresponding perrhenato complexes were obtained
in high yield (Eq. (4)):
NMR spectra are not helpful to identify these complexes
because there are no diagnostic groups present in these
complexes. The 13C-NMR spectra of the manganese
perrhenato complexes, 1 and 2, did not show any well-
[(CO)3(PꢀP)M]2fmOC(O)OgꢁRe2O7
0 2fac(CO)3(PꢀP)MOReO3 ꢁCO2
(4)
resolved resonances due to the terminal carbonyls (Cꢁ
/
We believe that first Re2O7 is converted to HReO4 by
adventitious water [5]. Then HReO4 reacts with
O)’s. However, the rhenium complexes, 3 and 4, showed
well-resolved carbonyl carbon resonances. For example,
the cis carbonyl carbon in 4 is observed at d 193.5 as a
triplet coupled to the two cis phosphorus atoms of the
dppp ligand with a coupling constant of 6 Hz; the
carbonyls trans to the corresponding phosphorus atoms
are observed at d 191.5 and 191.0 as triplets coupled to
two phosphorus atoms with a coupling constant of 23
Hz each.
[(CO)3(PꢀP)M]2{m-OC(O)O} to yield the corresponding
/
perrhenato complexes (Eq. (5)):
[(CO)3(PꢀP)M]2fmOC(O)Ogꢁ2HReO4
0 2fac(CO)3(PꢀP)MOReO3 ꢁCO2 ꢁH2O
(5)
In a separate experiment we observed that a dichlor-
P)M]2{m-OC(O)O} re-
acted rapidly with two equivalents of HReO4 to yield
omethane solution of [(CO)3(Pꢀ
/
the perrhenato complexes almost quantitatively.
2.2. Reactions of alkoxo manganese(I) and rhenium(I)
complexes, fac-(CO)3(Pꢀ
/P)MOR with Re2O7, where, R
2.5. Reactions of methoxymethyl complexes, fac-
is CH3 or CH2CH3
(CO)3(Pꢀ
/
P)MCH2OCH3 with Re2O7
When a mixture of the alkoxo complexes and Re2O7
(1:1 mol ratio) in dichloromethane was stirred, the
When an equimolar mixture of a methoxymethyl
complex, fac-(CO)3(PꢀP)MCH2OCH3 and Re2O7 in
/
corresponding perrhenato complexes, 1Á4 were ob-
/
dichloromethane was stirred, the corresponding perrhe-
nato complexes were obtained in moderate to high yield.
During the course of the reaction the color of the
solution changed from pale-yellow to red with simulta-
neous precipitation of some lower oxides of rhenium.
We did not attempt to study the mechanism of this
reaction. It is believed that Re2O7 ionizes in polar
solvents as ReO3ꢁReO4ꢂ. Therefore, it is possible that
tained in high yield. The reaction might proceed
according to Eq. (2):
fac(CO)3(PꢀP)MORꢁRe2O7
0 fac(CO)3(PꢀP)MOReO3 ꢁROReO3
(2)
The alkyl perrhenates, ROReO3, thus formed are
unstable [6]. The final products are black precipitates
presumed to be lower oxides of rhenium. The black
precipitates are not soluble in water or common organic
solvents. Similar black precipitates were also observed
during the preparation of Ta2(OMe)8(ReO4)2 from the
reaction of Ta2(OMe)10 with Re2O7 and confirmed by
SEM-EDS to be a rhenium-containing compound [7].
an intermediate carbene complex, [fac-(CO)3(Pꢀ
/
P)Mꢂ
/
CH2]ꢁ[ReO4]ꢂ is generated in the initial stage of the
reaction (Eq. (6)):
fac(CO)3(PꢀP)MCH2OCH3 ꢁRe2O7
0 [fac(CO)3(PꢀP)MꢂCH2]ꢁ[ReO4]ꢂ
ꢁCH3OReO3
(6)
2.3. Reactions of methylcarbonato complexes, fac-
(CO)3(Pꢀ/P)MOC(O)OCH3 with Re2O7
Alternatively, the carbene complexes may be formed
from O-protonation reaction of the methoxymethyl
When an equimolar mixture of a methylcarbonato
complex and Re2O7 in dichloromethane was stirred, the
corresponding perrhenato complex was obtained in high
complexes, fac-(CO)3(Pꢀ
/
P)MCH2OCH3 with HReO4
formed in situ from the reaction of Re2O7 with
adventitious water (Eq. (7)):

90
D.A. Brown et al. / Journal of Organometallic Chemistry 658 (2002) 88Á93
/
fac(CO)3(PꢀP)MCH2OCH3 ꢁHReO4
2.6. X-ray crystal structures of fac-(CO)3(dppp)-
0 [fac(CO)3(PꢀP)MꢂCH2]ꢁ[ReO4]ꢂ ꢁCH3OH (7)
MnOReO3 (2) and fac-(CO)3(dppp)ReOReO3 (4)
Similar O-protonation of methoxymethyl complexes
with acids are known. For example, the reaction of
(C5Me5)(dppe)FeCH2OMe with HBF4 was reported to
Crystal data for 2 and 4 were determined under the
conditions summarized in Table 1. The molecular plots
for 2 and 4 are provided in Fig. 1. Selected distances and
angles for 2 and 4 are provided in Table 2. As expected,
the central metal atom of 2 or 4 are octahedrally
coordinated to three terminal carbonyl ligands in a
facial arrangement, a bidentate dppp, and a monoden-
yield the carbene complex, [(C5Me5)(dppe)Feꢂ
/
CH2]ꢁ[BF4]ꢂ [8]. It is possible that the carbene com-
plexes decompose rapidly to afford the corresponding
perrhenato complexes (Eq. (8)):
2[fac(CO)3(PꢀP)MꢂCH2]ꢁ[ReO4]ꢂ
tate perrhenate anion. The Mnꢀ
/
OReO3 bond in 2 is
2.066(2) A which is slightly longer than the correspond-
˚
0 2[fac(CO)3(PꢀP)MOReO3 ꢁC2H4(?)
(8)
˚
ing distances of 2.020Á2.043(2) A reported for manga-
nese carboxylato complexes [11]. To the best of our
/
Similar decomposition of (CO)5ReCH2I was also
reported to yield C2H4 [9]. Among the starting materi-
als, the hydrido complexes are readily available [10].
Also the reactions of Re2O7 with the hydrido complexes
afforded reasonably good yields of the perrhenato
complexes. Therefore, the reaction noted in Eq. 1 is
the preferred method of synthesis of perrhenato com-
plexes.
knowledge, no manganese(I) perrhenato complex was
characterized previously by X-ray diffraction. The Reꢀ
/
˚
OReO3 bond distance of 2.175(3) A in 4 is comparable
to the corresponding distances of 2.152(4) [12] and
˚
2.207(3) A [13] reported for analogous rheniumÁper-
/
rhenato complexes. Similarly, the ReOꢀ
/ReO3 bond
˚
distance of 1.744(3) A in 4 is comparable to the
corresponding distances of 1.739(4) [12] and 1.754(3)
˚
A [13] reported for rheniumÁperrhenato complexes
Table 1
Summary of crystal data for fac-(CO)3(dppp)MnOReO3 (2) and fac-
(CO)3(dppp)ReOReO3 (4)
/
noted above. The Reꢀ
in 4 is comparable to the corresponding angles of 135Á
1648 reported for related rheniumÁperrhenato com-
plexes [14]. The MnꢀCO (trans) distance of 1.782(3) A
and ReꢀCO (trans) distance of 1.894(4) A are shorter
than their corresponding MꢀCO (cis) distances. Also
the MnCꢀO (trans) distance of 1.143(4) A and the
ReCꢀO (trans) distance of 1.151(5) A are longer than
the corresponding MꢀCO (cis) distances. Similar Mꢀ
CO (trans) bond shortening and MCꢀO (trans) bond
lengthening were observed in analogous rheniumÁper-
/
Oꢀ
/
Re angle of 153.1(2)8 observed
/
2
4
/
˚
/
Color and habit
Crystal size (mm)
Chemical formula
Orange prisms
0.18ꢃ0.32ꢃ0.38
Colorless prisms
0.15ꢃ0.15ꢃ0.08
C30H26O7P2Re2
9.7675(2)
˚
/
C
30H26MnO7P2Re
/
˚
a (A)
9.7779(2)
11.8671(2)
13.6100(2)
95.912(1)
90.387(1)
107.105(1)
1500.22(5)
0.71073
˚
/
˚
b (A)
˚
c (A)
11.9913(2)
13.6469(2)
96.773(1)
˚
/
a (8)
b (8)
g (8)
/
/
90.723(1)
/
107.168(1)
1514.62(5)
0.71073
/
3
˚
V (A )
rhenato complexes [12,13]. This is attributed to low
trans directing effect of the ReO4 ligand.
˚
Wavelength (A)
Crystal system
Space group
Z
Triclinic
¯
Triclinic
¯
P/1/
P/1/
2
2
Diffractometer
m (MoÁ )
Ka) (mmꢂ1
Scan mode
Nonius KappaCCD
4.603
Nonius KappaCCD
8.135
/
v, 18ꢃ800
v, 18ꢃ800
1.50ꢃ30.02
135h 513,
ꢂ165k 516,
05l 519
u Range (8)
Limiting indices
1.51Á27.47
/
ꢂ125h 512,
ꢂ155k 515,
05l 517
Absorption correction Gaussian
Gaussian
34 122
Reflections collected
Reflections/Rint
Reflections observed
Number of variables
R
30 513
6866 (0.0611)
6339; I ꢀ2s(I)
371
8801 (0.0556)
7507; I ꢀ2s(I)
371
a
a
a
0.0290 (0.0644)
0.0330 (0.0695)
0.0306 (0.0726)
0.0397 (0.0923)
a
Rw
Goodness-of-fit on F2 1.082
1.051
Full-matrix least-
squares on F2
Refinement method
Full-matrix least-
squares on F2
a
Definitions
of
R
and
.
Rw;
Rꢀa(jjF0jꢂjFcjj)/a(jF0j,
Rwꢀ[a(w(F20ꢂFc2)2/a w(F20)2]1/2
Fig. 1. The X-ray crystal structure of 2 or 4.

D.A. Brown et al. / Journal of Organometallic Chemistry 658 (2002) 88Á
/93
91
Table 2
Table 2 (Continued)
˚
Selected bond lengths (A) and bond angles (8) for fac-(CO)3(dppp)M-
nOReO3 (2) and fac-(CO)3(dppp)ReOReO3 (4)
2
4
2
4
C(12)ꢀC(7)ꢀP(1)
C(8)ꢀC(7)ꢀP(1)
120.0(2)
121.6(3)
122.7(2)
118.7(2)
118.4(3)
122.1(3)
123.0(3)
118.3(3)
C(12)ꢀC(7)ꢀP(1)
C(8)ꢀC(7)ꢀP(1)
119.7(3)
121.7(3)
122.9(3)
117.9(3)
118.5(4)
122.4(3)
122.5(3)
118.9(3)
Bond lengths
MnꢀC(1)
MnꢀC(2)
MnꢀC(3)
MnꢀO(4)
MnꢀP(1)
MnꢀP(2)
C(1)ꢀO(1)
C(2)ꢀO(2)
C(3)ꢀO(3)
ReꢀO(4)
ReꢀO(5)
ReꢀO(6)
ReꢀO(7)
P(1)ꢀC(4)
P(1)ꢀC(7)
P(1)ꢀC(13)
P(2)ꢀC(6)
P(2)ꢀC(19)
P(2)ꢀC(25)
C(18)ꢀC(13)ꢀP(1)
C(14)ꢀC(13)ꢀP(1)
C(24)ꢀC(19)ꢀP(2)
C(20)ꢀC(19)ꢀP(2)
C(30)ꢀC(25)ꢀP(2)
C(26)ꢀC(25)ꢀP(2)
C(18)ꢀC(13)ꢀP(1)
C(14)ꢀC(13)ꢀP(1)
C(24)ꢀC(19)ꢀP(2)
C(20)ꢀC(19)ꢀP(2)
C(30)ꢀC(25)ꢀP(2)
C(26)ꢀC(25)ꢀP(2)
1.782(3)
1.832(4)
1.823(4)
2.066(2)
2.3712(9)
2.3499(9)
1.143(4)
1.134(4)
1.134(5)
1.739(2)
1.683(4)
1.686(3)
1.694(4)
1.829(3)
1.827(3)
1.817(3)
1.830(3)
1.820(3)
1.833(3)
Re(1)ꢀC(1)
Re(1)ꢀC(2)
Re(1)ꢀC(3)
Re(1)ꢀO(4)
Re(1)ꢀP(1)
Re(1)ꢀP(2)
C(1)ꢀO(1)
C(2)ꢀO(2)
C(3)ꢀO(3)
Re(2)ꢀO(4)
Re(2)ꢀO(5)
Re(2)ꢀO(6)
Re(2)ꢀO(7)
P(1)ꢀC(4)
P(1)ꢀC(7)
P(1)ꢀC(13)
P(2)ꢀC(6)
P(2)ꢀC(19)
P(2)ꢀC(25)
1.894(4)
1.956(4)
1.963(5)
2.175(3)
2.4873(9)
2.4653(10)
1.151(5)
1.138(5)
1.122(6)
1.744(3)
1.677(6)
1.683(4)
1.699(5)
1.829(4)
1.831(4)
1.819(4)
1.833(4)
1.819(4)
1.828(4)
3. Conclusion
Transtion-metal (carbonyl) perrhenato complexes can
be easily synthesized from the reaction of Re2O7 with
the corresponding transition-metal (carbonyl) hydrido,
alkoxo, alkylcarbonato, carbonato-bridged, or alkoxy-
methyl complexes in CH2Cl2.
4. Experimental
Bond angles
C(1)ꢀMnꢀC(2)
C(1)ꢀMnꢀC(3)
C(2)ꢀMnꢀC(3)
C(1)ꢀMnꢀO(4)
C(2)ꢀMnꢀO(4)
C(3)ꢀMnꢀO(4)
C(1)ꢀMnꢀP(2)
C(2)ꢀMnꢀP(2)
C(3)ꢀMnꢀP(2)
O(4)ꢀMnꢀP(2)
C(1)ꢀMnꢀP(1)
C(2)ꢀMnꢀP(1)
C(3)ꢀMnꢀP(1)
O(4)ꢀMnꢀP(1)
P(2)ꢀMnꢀP(1)
O(1)ꢀC(1)ꢀMn
O(2)ꢀC(2)ꢀMn
O(3)ꢀC(3)ꢀMn
O(5)ꢀReꢀO(6)
O(5)ꢀReꢀO(7)
O(6)ꢀReꢀO(7)
O(5)ꢀReꢀO(4)
O(6)ꢀReꢀO(4)
O(7)ꢀReꢀO(4)
ReꢀO(4)ꢀMn
C(13)ꢀP(1)ꢀC(7)
C(13)ꢀP(1)ꢀC(4)
C(7)ꢀP(1)ꢀC(4)
C(13)ꢀP(1)ꢀMn
C(7)ꢀP(1)ꢀMn
C(4)ꢀP(1)ꢀMn
C(5)ꢀC(4)ꢀP(1)
C(6)ꢀC(5)ꢀC(4)
C(5)ꢀC(6)ꢀP(2)
C(19)ꢀP(2)ꢀC(6)
C(19)ꢀP(2)ꢀC(25)
C(6)ꢀP(2)ꢀC(25)
C(19)ꢀP(2)ꢀMn
C(6)ꢀP(2)ꢀMn
C(25)ꢀP(2)ꢀMn
88.6(2)
88.8(2)
89.4(2)
C(1)ꢀRe(1)ꢀC(2)
C(1)ꢀRe(1)ꢀC(3)
C(2)ꢀRe(1)ꢀC(3)
89.1(2)
89.5(2)
89.7(2)
All manipulations were carried out under a nitrogen
atmosphere and the solvents were dried prior to use.
Reagent grade chemicals were used without further
purification. Mn2(CO)10, Re2(CO)10, Re2O7, HReO4,
dppe, and dppp were obtained from commercial
176.92(13) C(1)ꢀRe(1)ꢀO(4)
89.26(14) C(2)ꢀRe(1)ꢀO(4)
178.3(2)
90.5(2)
92.1(2)
93.4(2)
C(3)ꢀRe(1)ꢀO(4)
92.66(11) C(1)ꢀRe(1)ꢀP(2)
91.59(12) C(2)ꢀRe(1)ꢀP(2)
178.26(12) C(3)ꢀRe(1)ꢀP(2)
93.91(13)
91.71(14)
176.32(14)
84.45(9)
97.69(13)
173.26(14)
90.43(14)
82.74(9)
87.78(3)
178.3(4)
178.4(4)
177.0(5)
110.7(3)
106.9(4)
110.1(3)
109.8(3)
110.4(2)
108.8(2)
153.1(2)
102.2(2)
106.1(2)
102.1(2)
117.57(12)
114.75(13)
112.45(13)
116.2(3)
114.5(4)
112.6(3)
105.2(2)
101.5(2)
101.4(2)
113.71(13)
112.29(13)
120.92(14)
sources. The starting materials, fac-(CO)3(Pꢀ
[10], fac-(CO)3(PꢀP)MOR 11c[15], fac-(CO)3(PꢀP)MO-
C(O)OR 11c, [(CO)3(PꢀP)M]2{m-OC(O)O} [16], and
fac-(CO)3(PꢀP)MCH2OCH3 [17] were synthesized ac-
cording to literature procedures.
IR spectra were recorded on a PerkinÁ
/P)MH
/
/
85.15(8)
O(4)ꢀRe(1)ꢀP(2)
/
98.00(11) C(1)ꢀRe(1)ꢀP(1)
173.21(12) C(2)ꢀRe(1)ꢀP(1)
89.40(12) C(3)ꢀRe(1)ꢀP(1)
/
84.15(7)
89.47(3)
176.0(3)
176.6(4)
175.4(4)
109.9(2)
107.6(3)
110.5(2)
110.1(2)
110.2(2)
108.6(2)
154.5(2)
O(4)ꢀRe(1)ꢀP(1)
P(2)ꢀRe(1)ꢀP(1)
O(1)ꢀC(1)ꢀRe(1)
O(2)ꢀC(2)ꢀRe(1)
O(3)ꢀC(3)ꢀRe(1)
O(5)ꢀRe(2)ꢀO(6)
O(5)ꢀRe(2)ꢀO(7)
O(6)ꢀRe(2)ꢀO(7)
O(5)ꢀRe(2)ꢀO(4)
O(6)ꢀRe(2)ꢀO(4)
O(7)ꢀRe(2)ꢀO(4)
Re(2)ꢀO(4)ꢀRe(1)
/Elmer 1600
series FTIR instrument. NMR spectra were recorded on
1
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. Microanalyses
were conducted by Quantitative Technologies Inc.
4.1. Reactions of hydrido manganese(I) and rhenium(I)
complexes, fac-(CO)3(Pꢀ/P)MH with Re2O7
101.79(14) C(13)ꢀP(1)ꢀC(7)
105.8(2)
101.4(2)
In a typical experiment a mixture of about 5 mmol of
fac-(CO)3(PꢀP)MH and 2.5 mmol of Re2O7 in 20 ml of
C(13)ꢀP(1)ꢀC(4)
C(7)ꢀP(1)ꢀC(4)
/
moist CH2Cl2 was allowed to stir for 30 min at ambient
temperature. The progress of the reaction was moni-
tored with IR. The solvent was removed on a rotary
118.39(10) C(13)ꢀP(1)ꢀRe(1)
114.71(11) C(7)ꢀP(1)ꢀRe(1)
112.82(11) C(4)ꢀP(1)ꢀRe(1)
115.9(2)
114.3(3)
112.2(2)
104.7(2)
100.9(2)
101.1(2)
C(5)ꢀC(4)ꢀP(1)
C(6)ꢀC(5)ꢀC(4)
C(5)ꢀC(6)ꢀP(2)
C(19)ꢀP(2)ꢀC(6)
C(19)ꢀP(2)ꢀC(25)
C(6)ꢀP(2)ꢀC(25)
evaporator. The residue was recrystallized in CH2Cl2Á
hexane at ꢂ5 8C. Filtration afforded colorless to pale-
yellow crystals of perrhenato complexes, fac-(CO)3(Pꢀ
P)MOReO3 (1, MꢀMn, PꢀPꢀdppe; 2, MꢀMn, Pꢀ
Pꢀdppp; 3, MꢀRe, PꢀPꢀdppe; 4, MꢀRe, PꢀPꢀ
197 8C with
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
113.10(12) C(19)ꢀP(2)ꢀRe(1)
112.79(11) C(6)ꢀP(2)ꢀRe(1)
122.15(12) C(25)ꢀP(2)ꢀRe(1)
dppp). Data for 1: yield, 72%; m.p. 195Á
/
decomposition. IR (cmꢂ1, CH2Cl2): n(CO) 2034s,
1966s, 1930s; n(ReO) 931m, 900m. 1H-NMR (d,

92
D.A. Brown et al. / Journal of Organometallic Chemistry 658 (2002) 88Á93
/
CD2Cl2): 7.68Á
NMR (d, CD2Cl2): 214.8 (s, br, CO), 134.0Á
C6H5), 25.8(t, J 18 Hz, ꢀPCH2) Anal. Calc. for
C29H24MnO7P2Re: C, 44.2; H, 3.1. Found: C, 44.4; H,
/
7.18 (m, 20H), 3.0Á
/
2.68 (m, 4H). 13C-
129.7 (m,
black precipitates were observed. The solvent was
removed on a rotary evaporator. The residue was
/
/
recrystallized in CH2Cl2Á
afforded colorless to pale-yellow crystals of the per-
rhenato complexes, fac-(CO)3(PꢀP)MOReO3, 1Á4, in
78Á83% yield.
/
hexane at ꢂ5 8C. Filtration
/
3.2%. Data for 2: yield, 76%; m.p. 185Á186 8C with
/
/
/
decomposition. IR (cmꢂ1, CH2Cl2): n(CO) 2038 s, 1972
/
1
s, 1925 s; n(ReO) 928 m, 910 m. H-NMR (d, CD2Cl2):
7.56Á
CD2Cl2): 215.2 (s, br, CO), 135.6Á
25.1(t, J 12 Hz, ꢀPCH2), 18.9 (s, H2CCH2CH2). Anal.
Calc. for C30H26MnO7P2Re: C, 44.9; H, 3.3. Found: C,
/
7.34 (m, 20H), 2.52Á
1.54 (m, 6H). 13C-NMR (d,
/
/
129.4 (m, C6H5),
4.4. Reactions of carbonato-bridged complexes,
[(CO)3(PꢀP)M]2{m-OC(O)O} with Re2O7
/
/
44.6; H, 3.3%. Data for 3: yield, 87%; m.p. 190Á193 8C
/
In a typical experiment an equimolar mixture of
Re2O7 and [(CO)3(dppe)Mn]2{m-OC(O)O}, [(CO)3-
with decomposition. IR (cmꢂ1, CH2Cl2): n(CO) 2038s,
1962s, 1920s; n(ReO) 933m, 910m. 1H-NMR (d,
(dppp)Mn]2{m-OC(O)O},
or
[(CO)3(dppe)Re]2{m-
CD2Cl2): 7.79Á
NMR (d, CD2Cl2): 193.0 (dd, 9Hz, 60 Hz, 2CO),191.2(t,
8 Hz, CO), 132.7Á128.1(m, C6H5), 26.6(m,ꢀPCH2).
Anal. Calc. for C29H24O7P2Re2: C, 37.9; H, 2.6. Found:
/
7.24 (m, 20H), 3.08Á
/
2.62 (m, 4H). 13C-
OC(O)O} in 10 ml of moist CH2Cl2 was allowed to
stir at ambient temperature for 30 min. The progress of
the reaction was monitored with IR. The solvent was
removed on a rotary evaporator. The residue was
/
/
C, 37.9; H, 2.6%. Data for 4: yield, 88%; m.p. 250Á
/
252 8C with decomposition. IR (cmꢂ1, CH2Cl2):
n(CO) 2041s, 1965s, 1915s; n(ReO) 955m, 935m. H-
recrystallized in CH2Cl2Á
afforded colorless to pale-yellow crystals of the per-
rhenato complexes, fac-(CO)3(PꢀP)MOReO3, 1Á3, in
80Á85% yield.
/
hexane at ꢂ5 8C. Filtration
/
1
/
/
NMR (d, CD2Cl2): 7.55Á
6H). 13C-NMR (d, CD2Cl2): 193.5 (t, 6 Hz, CO), 191.5
(t, 23 Hz, CO), 191.0 (t, 23 Hz, CO), 134.9Á129.6 (m,
C6H5), 25.2(t, J 13 Hz, ꢀPCH2), 19.6 (s, H2CCH2CH2).
/
7.35 (m, 20H), 2.70Á
/
1.74 (m,
/
/
/
Anal. Calc. for C30H26O7P2Re2: C, 38.6; H, 2.8. Found:
C, 38.6; H, 2.8%.
4.5. Reactions of methoxymethyl complexes, fac-
(CO)3(PꢀP)MCH2OCH3 with Re2O7
/
4.2. Reactions of alkoxo manganese(I) and rhenium(I)
In a typical experiment a mixture of about 2 mmol of
fac-(CO)3(PꢀP)MCH2OCH3 and 2 mmol of Re2O7 in
10 ml of CH2Cl2 was allowed to stir at 0 8C for 30 min.
The progress of the reaction was monitored with IR. A
black precipitate was also observed in this reaction. The
solvent was removed on a rotary evaporator. The
complexes, fac-(CO)3(Pꢀ
/P)MOR with Re2O7, where, R
/
is CH3 or CH2CH3
In a typical experiment a mixture of about 2 mmol of
fac-(CO)3(PꢀP)MOCH3 and 2 mmol of Re2O7 in 10 ml
/
of CH2Cl2 was allowed to stir for 30 min at ambient
temperature. The progress of the reaction was moni-
tored with IR. During this period the color of the
solution changed from yellow (alkoxo manganese com-
plexes) or colorless (alkoxo rhenium complexes) to dark
red and black precipitates were observed. The solvent
was removed on a rotary evaporator and the residue was
extracted with 20 ml of CH2Cl2. The solution was
evaporated to dryness and the residue was recrystallized
residue was recrystallized in CH2Cl2Á
5 8C. Filtration afforded colorless to pale-yellow crys-
/
hexane at ꢂ
/
tals of the perrhenato complexes, fac-(CO)3(Pꢀ
/
P)MOReO3, 1Á
/
4, in 69Á76% yield.
/
4.6. X-ray crystal structure of fac-
(CO)3(dppp)MnOReO3 (2)
in CH2Cl2Á
less to pale-yellow crystals of the perrhenato complexes,
fac-(CO)3(PꢀP)MOReO3, 1Á4, in 81Á85% yield.
/
hexane at ꢂ5 8C. Filtration afforded color-
/
Crystals of 2 were grown from CH2Cl2Á
/
hexane on
cooling at ꢂ
/
5 8C. Data were collected on a Nonius
/
/
/
KappaCCD diffractometer and corrected for Lorentz-
polarization and absorption effects. The structure was
direct methods and refined by full-matrix least-squares
on F2 using SHELXTL (version 5.04). The non-hydrogen
atoms were refined anisotropically and the hydrogens
were allowed to ride on their respective carbons. The
hydrogens were assigned isotropic displacement coeffi-
4.3. Reactions of methylcarbonato complexes, fac-
(CO)3(PꢀP)MOC(O)OCH3 with Re2O7
/
In a typical experiment a mixture of about 2 mmol of
fac-(CO)3(PꢀP)MOC(O)OCH3 and 2 mmol of Re2O7 in
/
10 ml of CH2Cl2 was allowed to stir at 0 8C for 30 min.
The progress of the reaction was monitored with IR.
During the course of the reaction the color of the
solution changed from yellow or colorless to red and
cients U(H)ꢀ1.2U(C) and an extinction parameter was
/
included in the refinements. Similar methods were used
for 4, which is isomorphous with 2.

D.A. Brown et al. / Journal of Organometallic Chemistry 658 (2002) 88Á
/93
93
[3] D. Brown, L.P. Brown, S.K. Mandal, 216th ACS National
Meeting, Boston, Massachusetts, 23Á27 August, 1998, Abstr.
No. 100.
5. Supplementary material
/
The following crystal structures have been deposited
at the Cambridge Crystallographic Data Centre and
allocated the deposition numbers CCDC 162600 for
compound 2 and CCDC 162601 for compound 4.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
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