The preparation and reactions of the azides of fac-Mn(CO)3(P-P)N3. The X-ray crystal structures of fac-[Mn(CO)3(P-P)(OH2)]BF4, fac-Mn(CO)3(P-P)(NN2C(CF3)N) [(P-P)=dppe and depe], and fac-[Mn(CO)3(depe)(PPh3)]BF4

Article abstract of DOI:10.1016/S0277-5387(99)00161-8

A simple three-step, high-yield synthesis of the titled azides from Mn₂(CO)₁₀ and P-P is described involving the intermediate aqua complexes, fac-[Mn(CO)₃(P-P)(H₂O)]BF₄, 3a,b. The aqua ligand is very labile; it is easily exchanged for D₂O, PPh₃, and NO₂^-. Crystal structures of the two titled aqua complexes and fac-[Mn(CO)₃(depe)(PPh₃)]BF₄, 6a, are reported. The aqua complexes react instantaneously with aqueous NaN₃ to give quantitative yields of the corresponding covalent azides which undergo the expected 1,3-dipolar additions with CF₃CN to give the corresponding tetrazoles whose crystal structures are also reported. Elsevier Science Ltd.

Full text of DOI:10.1016/S0277-5387(99)00161-8

Polyhedron 18 (1999) 2563–2571
The preparation and reactions of the azides of fac-Mn(CO)3(P-P)N3.
The X-ray crystal s%tr%u%ct%u%re%s%%of%fac-[Mn(CO) (P-P)(OH )]BF ,
3
2
4
%
4
4
fac-Mn(CO)3(P-P)(NN2C(CF3)N) [(P-P)5dppe and depe], and
fac-[Mn(CO)3(depe)(PPh3)]BF4
*
Thomas M. Becker, Jeanette A. Krause-Bauer, Craig L. Homrighausen, Milton Orchin
Department of Chemistry, University of Cincinnati, Cincinnati OH 45221-0172, USA
Received 4 March 1999; accepted 28 May 1999
Abstract
A simple three-step, high-yield synthesis of the titled azides from Mn2(CO)10 and P-P is described involving the intermediate aqua
complexes, fac-[Mn(CO)3(P-P)(H2O)]BF4, 3a,b. The aqua ligand is very labile; it is easily exchanged for D2O, PPh3, and NO22 . Crystal
structures of the two titled aqua complexes and fac-[Mn(CO)3(depe)(PPh3)]BF4, 6a, are reported. The aqua complexes react
instantaneously with aqueous NaN3 to give quantitative yields of the corresponding covalent azides which undergo the expected
1,3-dipolar additions with CF3CN to give the corresponding tetrazoles whose crystal structures are also reported.
Science Ltd. All rights reserved.
1999 Elsevier
Keywords: Manganese complexes; Aqua complexes; Crystal structures; Tetrazolato complexes; Azido complexes; 1,3-Dipolar cycloadditions
1. Introduction
2. Experimental
Our previously reported synthesis of the azides, fac-
Mn(CO)3(P-P)N3, P-P51,2-bis(diethylphosphino)ethane
(depe) and 1,2-bis(diphenylphosphino)ethane (dppe), 4a,b,
involved reacting the corresponding chloro complexes,
fac-Mn(CO)3(P-P)Cl, 2a,b, with NaN3 in a very slow
reaction (30–40 days at room temperature) [1]. A vastly
improved route, described herein, starts with the now
readily available hydrides, fac-Mn(CO)3(P-P)H [2,3],
1a,b, and reacting these with HBF4 to give the ionic aqua
complexes fac-[Mn(CO)3(P-P)(H2O)]BF4, 3a,b, which
then react almost instantaneously with aqueous NaN3 to
give the desired azides. Alternatively, the azides can be
prepared by reaction of the chloro complexes, 2a,b, with
the expensive AgBF4 followed by treatment with NaN3.
The availability of the azides provides a convenient route
to the corresponding triazoles [1] (via the 1,3-dipolar
reaction with acetylenes) and tetrazoles (via reaction with
nitriles).
All reactions were carried out under an argon atmos-
phere using a Schlenk line. Solvents were used as received
unless otherwise noted. Dppe and depe were purchased
from Pressure Chemicals. AgBF4, PPh3 and HBF4?Et2O
(54% w/w solution) were purchased from Aldrich. CF3CN
was purchased from Lancaster Synthesis. Fac-
Mn(CO)3(P-P)H (1a,b)(a5depe, b5dppe), and fac-
Mn(CO)3(P-P)Cl (2a,b)(a5depe, b5dppe) were prepared
according to literature methods [1–4]. Complex 1a was
isolated as a solid from 1-propanol. IR spectra were
recorded on a Perkin–Elmer 1600 series FT–IR instrument
1
employing 1.0 mm NaCl liquid cells unless noted. H
NMR were recorded using a Bruker AC-250 spectrometer
with CDCl3 chemical shifts recorded relative to Me4Si.
Melting points were obtained using a Mel-Temp apparatus
and are uncorrected. Elemental analysis were performed by
Galbraith Laboratories. High resolution mass spectra were
recorded on a Kratos-80.
2.1. Preparation of fac-[Mn(CO)3(P-P)(OH2 )]BF4 (3a,b)
(a5depe, b5dppe)
*Corresponding author.
E-mail address: orchinm@uc.edu (M. Orchin)
The hydride, 1a (0.182 g, 0.526 mmol) was dissolved
0277-5387/99/$ – see front matter
PII: S0277-5387(99)00161-8
1999 Elsevier Science Ltd. All rights reserved.

2564
T.M. Becker et al. / Polyhedron 18 (1999) 2563–2571
%4 %%%%%4
2.3. Preparation of fac-Mn(CO)3(P-P)(NN2C(CF3 )N)
(5a,b) (a5depe, b5dppe)
with stirring in 25 ml of chloroform. HBF4?Et2O (0.090
ml, 0.653 mmol) was syringed into the flask whereupon
dihydrogen gas was immediately evolved. After a 15-min
stir, the solvent was removed via rotary evaporator. The
residue was stirred with 233 ml of Et2O and the ether
decanted from the oily brown solid in order to remove any
excess HBF4. Hexane was added, the mixture stirred, and
the hexane was removed yielding the yellow solid 3a
(0.194 g, 83% yield).
The azide 4a (0.215g, 0.555 mmol) was added to a flask
with 20 ml of CH2Cl2. The solution was stirred and
CF3CN was bubbled through the solution (approximately 5
min). The sealed solution was stirred for 2d and during that
period the solution was resaturated twice with CF3CN. The
solvent was removed using a rotary evaporator. The
solution was redissolved in CH2Cl2 and filtered through
glass wool. After solvent removal, the residue was re-
dissolved in benzene/hexane and then cooled, whereupon
pale yellow X-ray quality crystalline solid tetrazole pre-
cipitated, 5a (0.087g, 30.8% yield).
The yellow solid 3b (0.856 g, 89% yield) was isolated
from the reaction of the hydride 1b (0.807 g, 1.50 mmol)
with HBF4?Et2O (0.25 ml, 1.81 mmol) in 50 ml of CHCl3
in a manner similar to that described above for 3a.
In another procedure, the aqua complexes 3a and 3b
were prepared from the reactions of the chloro complexes
2a and 2b, respectively, with a slight excess of AgBF4
(1:1.2 molar ratio). Both reactions were complete within 1
h of stirring in chloroform. Filtration through a medium
frit removed excess AgBF4 and AgCl. Prolonged stirring
(over 4 h) over the silver salts resulted in some decomposi-
tion and increasing amounts of [Mn(CO)4(P-P)]BF4 [5].
X-ray quality crystals of 3a were grown from CHCl3 /
Et2O and 3b crystals were grown from CHCl3 /hexane.
Aqua complex 3b crystallizes with one molecule of water
in the lattice.
X-ray quality crystals of the pale yellow tetrazole, 5b,
were obtained when the azide, 4b (0.191 g, 0.330 mmol),
was stirred in CH2Cl2 saturated with CF3CN for 6 days.
The tetrazole, 5b, crystallizes from benzene/hexane with
one molecule of benzene in the lattice.
Data 5a: m.p. 133–1348C. IR (cm21, CH2Cl2): n(CO)
1
2029, 1958, 1917; n(C5N) 1606. H NMR (d, CDCl3):
2.31–1.67 (m, 12 H, CH2), 1.25–0.82 (m, 12H, CH3).
Found: C, 36.8; H, 5.5; N, 11.0. Calc. for
C15H24F3MnN4O3P2: C, 37.4; H, 5.0; N, 11.6.
Data 5b: m.p. 95–1008C (turns opaque), 206–2108C
(melt). IR (cm21, CH2Cl2): n(CO) 2032, 1963, 1936. 1H
NMR (d, CDCl3): 7.55–7.13 (m, 20H, Ph), 3.50–2.93 (m,
4H, CH2) Found: C, 58.1; H, 4.2; N, 7.5. Calc. for
C31H24F3MnN4O3P2?C6H6: C, 59.1; H, 4.0; N, 7.4.
Data 3a: m.p. 135–1388C. IR (cm21, CHCl3): n(CO)
1
2031, 1958, 1917. H NMR (d, CDCl3): 2.78 (s, br, 2H,
H2O) (D2O exchangeable), 1.98 (m, 12H, CH2), 1.25 (m,
12H, CH3). MS (m/z): 345 [Mn(CO)3(depe)]1. Found: C,
34.5; H, 5.9. Calc. for C13H26BF4MnO4P2: C, 34.7; H, 5.8.
Data 3b: m.p. 150–1538C. IR (cm21, CHCl3): n(CO)
2033, 1962, 1934. 1H NMR (d, CDCl3): 7.54 (m, 20H, Ph),
2.98 (m, 4H, CH2), 2.03 (s, br, 2H, OH2) (D2O exchange-
able). MS (m/z): 537 [Mn(CO)3(dppe)]1, 453
[Mn(dppe)]1. Found: C, 52.3; H, 4.5. Calc for
C29H26BF4MnO4P2?H2O: C, 52.8; H 4.3.
2.4. Preparation of [fac-Mn(CO)3(P-P)(PPh3 )]BF4
(6a,b) (a5depe, b5dppe)
The aqua complex, 3a, was prepared from the reaction
of the chloride, 2a (0.216 g, 0.567 mmol), with AgBF4
(0.134 g, 0.688 mmol) in chloroform as described above.
After filtration of the silver salts, PPh3 (0.148 g, 0.564
mmol) was added and the solution stirred for 10 min after
which it was concentrated using a rotary evaporator. Et2O
was then added and the solution was cooled whereupon
0.314 g (79.8% yield) of the yellow solid 6a precipitated.
X-ray quality crystals of 6a were grown from CHCl3 /
Et2O.
2.2. Preparation of fac-Mn(CO)3(P-P)N3 (4a,b) (a5
depe, b5dppe)
The aqua complex 3a (0.028 g, 0.062 mmol) was added
to 15 ml of CHCl3. Excess NaN3(aq) (ca. 20 drops of a
saturated NaN3(aq) solution) was added and the mixture
stirred for 20 min. The solvent was removed by a rotary
evaporator followed by high vacuum to remove any water.
The solids were taken up in CH2Cl2 and filtered through a
small quantity of silica gel over glass wool to remove any
excess NaN3. Hexane was added and the solvents removed
via rotary evaporator giving the yellow solid azide, 4a
(0.020 g, 83% yield). The spectroscopic data matched
those previously reported [1].
The azide 4b was isolated in a manner similar to that
described above. The aqua complex 3b (0.031 g, 0.048
mmol) was stirred with 20 drops of NaN3(aq) to produce
4b (0.028 g, 100% yield). The spectroscopic data matched
those previously reported [1].
Complex 6b was prepared in a manner similar to
complex 6a. 2b (0.206 g, 0.360 mmol), AgBF4 (0.083 g,
0.426 mmol) and PPh3 (0.095 g, 0.362 mmol) were
employed. The stirring time after PPh3 addition was 20
min. The solvent was removed using a rotary evaporator
and the yellow solid 6b was obtained without further
purification (0.286 g, 99% yield).
Data 6a: m.p. 138–1408C. IR (cm21, CHCl3): n(CO)
1
2024, 1954, 1903. H NMR (d, CDCl3): 7.52–7.19 (m,
15H, Ph), 3.01–1.80 (m, 12H, CH2), 1.24–0.84 (m, 12H,
CH3). MS (m/z): 607 ([Mn(CO)3(depe)(PPh3)]1), 523
([Mn(depe)(PPh3)]1), 345 ([Mn(CO)3(depe)]1), 261
([Mn(depe)]1).
Found:
H.
5.4.
Calc.
for

T.M. Becker et al. / Polyhedron 18 (1999) 2563–2571
2565
C31H29BF4MnO3P3: C, 53.6; H, 5.7. Analysis for carbon
was unsatisfactory.
held fixed in 3a. The H-atom positions for the solvent were
also held fixed. All other hydrogens were either located
directly or calculated based on geometric criteria and
treated with a riding model. Uiso for all H-atoms was
defined as U(H)5a*U(C,O) where a51.5 for methyl or
O-H and 1.2 for the remaining hydrogens. Final crystallo-
graphic agreement factors are summarized in Table 1.
The BF4 anions in 3a and 3b are disordered, the refined
occupancies for the major conformation range from 50.5–
57.3% for 3a and 50.6–69.5% for 3b. Complex 6a
crystallizes as two independent molecules differing by
torsion angles. The two independent BF4 anions in 6a are
disordered over two principal conformations, occupancy
set at 0.5 and F atom displacement parameters of the
second BF4 were restrained to be equal those of the first.
Compound 5b crystallizes with one disordered benzene,
occupancy was set at 0.5 for each conformation. In 5a and
5b, the CF3 group is highly disordered. Two conforma-
tions with occupancies set at 0.5 were defined and used in
subsequent refinements. However electron density appears
in nearly a continuous ring about C6 at appropriate C–F
distances, indicative of numerous CF3 conformational
possibilities. In 5b the anisotropic displacement parameters
for F4–F6 were set equivalent to the better behaved F1–F3
Data 6b: m.p. 118–1238C. IR (cm21, CHCl3): n(CO)
1
2030, 1961, 1933. H NMR (d, CDCl3): 7.67–6.76 (m,
35H, Ph), 3.5–2.35 (m, 4H, CH2). MS (m/z): 799
([Mn(CO)3(dppe)(PPh3)]1), 715 ([Mn(dppe)(PPh3)]1),
537 ([Mn(CO)3(dppe)]1), 453 ([Mn(dppe)]1). Found: H,
4.45. Calc. for C47H39BF4MnO3P3: C, 63.7; H, 4.43.
Analysis for carbon was unsatisfactory.
2.5. Preparation of fac-Mn(CO)3(depe)NO2 (7)
The aqua complex, 3a, was prepared from the reaction
of the chloro complex, 2a, (0.210 g, 0.552 mmol) with
AgBF4 (0.133 g, 0.683 mmol) in chloroform as described
above. After filtration of the silver salts, excess NaNO2
(0.127 g, 1.84 mmol) was added and the mixture stirred
for 24 h after which it was filtered through a frit to remove
NaBF4 and excess NaNO2. The solvent was removed
using a rotary evaporator leaving the yellow solid, 7 (0.180
g, 83% yield).
Data 7: m.p. 86–898C. IR (cm21, CHCl3): n(CO)
1
2029s, 1962s, 1923s. H NMR (d, CDCl3): 2.3–1.9 (m,
12H, CH2), 1.2–0.92 (m, 12H, CH2) MS (m/z): 391
([Mn(CO)3(depe)NO2]1), 345 ([Mn(CO)3(depe)]1).
Found: C, 39.7; H 6.5. Calc. for C13H24MnNO5P2: C,
39.9; H, 6.2.
parameters. A final difference Fourier map for 6a showed
23
˚
two residual electron density peaks, 1.10 and 1.02 eA
,
˚
within 1.5A from C9A and C2B/O2B, respectively, but
not reasonable in terms of bonding geometry.
2.6. Crystal structure determinations of 3a, 3b, 5a, 5b,
and 6a
3. Results and discussion
Crystals of 3b were very fragile therefore a more
appropriate size could not be cut without damaging the
specimen. A suitable crystal of 5b was mounted in a glass
capillary since it was readily prone to solvent loss. All
other compounds were either of appropriate size or could
be cut from a larger specimen and mounted without
difficulty.
The introduction of nucleophilic ligands onto the metal
of coordination complexes is frequently achieved by
displacement of weakly coordinating anions which act as
excellent leaving groups [7]. This strategy has been
utilized with Mn and Re carbonyl systems with leaving
groups such as BF4 [8–14], AsF6 [14,15], PF6 [8–
12,16,17], ClO4 [5,16–18], O3SCF3 [19], and OTeF5
[20,21]. In our laboratory, we usually introduce the BF4
ligand by reacting Mn–H complexes with HBF4. This is a
particularly attractive route because the hydrides fac-
Mn(CO)3(P-P)H, 1a,b, can be prepared in one step from
Mn2(CO)10 and P-P in refluxing 1-pentanol [3]. It is
usually accepted that the initial product formed in the
reaction of such hydrides with HBF4 is the covalent
MnFBF3 species which is then readily displaced by other
ligands. Thus, e.g., the preparation of [Mn(CO)4(P-P)]BF4
is achieved by simply bubbling CO into a CH2Cl2 solution
of what is assumed to be the covalent complex
Mn(CO)3(P-P)FBF3 prepared from fac-Mn(CO)3(P-P)H,
1a,b, and HBF4 [3]. In the course of developing our new
improved route to the azides, we now have reason to
believe that the covalent complex is not the compound
undergoing substitution, but that instead it is the ionic aqua
complex fac-[Mn(CO)3(P-P)(H2O)]BF4, 3a,b. We have
Lattice parameters for 3b were obtained from reflections
lying in a 2u range of 10–308. A hemisphere of data was
collected using u–2u scans on a P3 diffractometer. Intensi-
ty data for the other crystals were collected on a CCD
diffractometer with a detector distance of 5.0 cm. A series
of data frames measured at 0.38 in v were collected to
calculate a unit cell. Depending on the crystal symmetry,
either a hemisphere or full sphere of frames (v scan mode)
were collected. All data were corrected for decay, Lorentz
and polarization as well as absorption effects [6].
All structures were refined by full-matrix least squares
on F2. Non-hydrogen atoms were refined with anisotropic
displacement parameters. Weights were assigned as w21
5
s2(Fo2)1(aP)21bP where P50.33333Fo210.66667F2c.
Hydrogen atoms bound to the aqua ligand and the solvent
in 3a and 3b were located directly from the difference
map, the aqua H-atom positions were refined in 3b but

2566
T.M. Becker et al. / Polyhedron 18 (1999) 2563–2571
Table 1
Crystal data
Compound
3a
3b
5a
5b
6a
Formula
[C13H26O4P2Mn]BF4 [C29H26O4P2Mn]BF4?H2O C15H24F3N4O3P2Mn C31H24F3N4O3P2Mn?C6H6 [C31H39O3P3Mn]BF4
Formula weight
Color/morphology
Crystallization solvent CHCl3 –Et2O
450.03
Yellow plate
660.20
482.26
752.53
694.28
Yellow plate
CHCl3 –hexane
0.9030.8030.35
298
Siemens P3
0.71073
Pale yellow plate
C6H6 –hexane
0.4030.3030.10
298
Siemens CCD
0.71073
Pale yellow plate
C6H6 –hexane
0.45x0.40x0.25
250
Siemens CCD
0.71073
Yellow plate
CHCl3 –Et2O
0.60x0.50x0.25
223
Siemens CCD
0.71073
Crystal size, mm
Temperature, K
Diffractometer
0.4030.2530.08
223
Siemens CCD
0.71073
˚
Wavelength, A
Crystal system
Space group
Z
Triclinic
P-1
2
Triclinic
P-1
2
Monoclinic
P21 /n
4
15.438(1)
8.846(1)
15.966(1)
Monoclinic
C2/c
8
36.741(7)
9.557(2)
21.827(4)
Triclinic
P-1
4
˚
a, A
7.9995(3)
11.4260(4)
12.6466(5)
104.755(1)
103.375(1)
105.360(1)
1021.05(7)
28.27
11.467(2)
11.682(2)
13.869(3)
71.41(3)
88.04(3)
61.71(3)
1535.2(5)
27.56
13.404(1)
15.222(1)
18.021(1)
99.50(1)
105.58(1)
100.77(1)
3388.2(4)
28.21
˚
b, A
˚
c, A
a, 8
b, 8
g, 8
94.79(1)
107.61(3)
3
˚
Volume, A
2172.8(3)
29.81
7305(3)
28.25
umax, 8
Transmssn, min/max
Absorption method
Initial solution
Reflects collected
Unique reflects
Rint
0.7007/0.8558
Multi-scan
Direct methods
11207
4952
0.0244
0.5851/0.7318
Psi scans
Patterson
7415
7060
0.0124
0.7112/0.9280
Multi-scan
Direct methods
15158
5672
0.0278
0.7475/0.9280
Multi-scan
Patterson
22877
8948
0.0547
0.6691/0.8245
Multi-scan
Patterson
36300
16215
0.0262
Reflects.2s(I)
No. parameters
4100
266
5914
425
3705
280
5282
514
11941
784
Final R with I.2s(I) R150.0349
wR250.0756
R150.0400
wR250.1009
R150.0666
wR250.1583
R150.0349
wR250.0772
R150.0682
wR250.0888
R150.0455
wR250.0968
R150.0980
wR250.1154
R150.0616
wR250.1539
R150.0885
wR250.1780
Final R all dataa
R150.0480
wR250.0819
a R(F2)5SuFo22Fc2u/SuF2ou; wR5Sw1 / 2(uFo22F2cu)/Sw1 / 2uFo2u
isolated these aqua complexes and report their crystal
structures below. All attempts to avoid the formation of the
aqua complex by careful removal of all water were
unsuccessful. The effect of adventitious water and the great
difficulty of removing it have been observed in analogous
reactions [22]. The aqua complexes, 3a,b, react almost
instantaneously with aqueous sodium azide to give the
manganese azides, 4a,b, in essentially quantitative yields.
Attempts to remove coordinated water from the ionic
complex by azeotroping with benzene were unsuccessful
as were efforts to force BF4 into the covalent complex by
refluxing a benzene solution of the aqua complex in the
presence of (C2H5)4NBF4. The aqua complexes are re-
markably reactive towards substitution, e.g., by chloride. If
traces of water are present in IR samples using a NaCl cell,
the observed spectrum is that of the corresponding chloro
complex, 2a,b, owing to the small quantity of dissolved
chloride. Such a reaction was confirmed by treating CHCl3
solutions of the aqua complexes with a few drops of
aqueous NaCl whereupon the corresponding chloro com-
plexes are immediately formed. NMR examination of the
aqua complexes, 3a,b, show rapid exchange with D2O. We
have taken advantage of the reactivity of the aqua com-
plexes by preparing the PPh3 derivatives, 6a,b, a NO2
derivative, 7, and are now exploring other replacement
reactions.
The ready availability of the azides, 4a,b, invites an
exploration of a variety of reactions with them. We
reported on their reactions in a 1,3-dipolar fashion with
acetylenes to give triazoles [1] and now have extended this
Fig. 1. Ortep diagram of fac-[Mn(CO)3(depe)(OH2)]BF4, 3a, indicating
labeling scheme and 50% thermal ellipsoids.

T.M. Becker et al. / Polyhedron 18 (1999) 2563–2571
2567
Fig. 2. Ortep diagram of fac-[Mn(CO)3(dppe)(OH2)]BF4, 3b, indicating labeling scheme and 50% thermal ellipsoids.
reaction. We now also report that CF3CN reacts with the
azide complexes, 4a,b, in a similar fashion to give the
corresponding tetrazolato complexes, 5a,b. Addition re-
actions using other nitriles (aceto-, benzo-, pyruvo-,
malono-, acrylo-) were attempted but were unsuccessful. In
an earlier paper we reported on the effect on the infrared
spectra in the carbonyl region of substituents on the
phosphorous atom in the chelating ligands. Such trends
were found to apply to the new complexes reported here
[1].
3.1. Crystal structures of 3a, 3b, 5a, 5b, 6
Crystallographic data for complexes 3a, 3b, 5a, 5b, and
6 are summarized in Table 1. The molecular structures of
the aqua complexes 3a and 3b are found in Figs. 1 and 2
Table 2
˚
Bond lengths (A) and angles (8) for 3a
Mn–C(2)
Mn–C(1)
Mn–P(1)
O(1)–C(1)
O(3)–C(3)
O(4)–H(4B)
1.768(2)
1.838(2)
2.326(1)
1.141(3)
1.141(3)
0.89
Mn–C(3)
Mn–O(4)
Mn–P(2)
O(2)–C(2)
O(4)–H(4A)
1.838(2)
2.115(2)
2.328(1)
1.160(3)
0.85
C(2)–Mn–C(3)
C(3)–Mn–C(1)
C(3)–Mn–O(4)
C(2)–Mn–P(1)
C(1)–Mn–P(1)
C(2)–Mn–P(2)
C(1)–Mn–P(2)
P(1)–Mn–P(2)
Mn–O(4)–H(4B)
O(1)–C(1)–Mn
O(3)–C(3)–Mn
89.50(10)
92.77(9)
93.72(9)
93.27(7)
174.22(7)
87.89(7)
92.17(6)
83.59(2)
120
C(2)–Mn–C(1)
C(2)–Mn–O(4)
C(1)–Mn–O(4)
C(3)–Mn–P(1)
O(4)–Mn–P(1)
C(3)–Mn–P(2)
O(4)–Mn–P(2)
Mn–O(4)–H(4A)
H(4A)–O(4)–H(4B)
O(2)–C(2)–Mn
90.48(10)
175.65(8)
92.28(8)
91.66(7)
83.72(4)
174.44(7)
88.64(4)
121
104
179.3(2)
177.5(2)
174.3(2)
Hydrogen bonding interactions
˚
H . . . F Distance (A)
Angle (8)
156.1(6)
153.0(2)
150.2(2)
169.4(5)
173(2)
O(4)–H(4A) . . . F(5)1
O(4)–H(4A) . . . F(3)1
O(4)–H(4A) . . . F(1)1
O(4)–H(4B) . . . F(4)2
O(4)–H(4B) . . . F(8)2
1.96
2.07
2.48
1.80
1.81

2568
T.M. Becker et al. / Polyhedron 18 (1999) 2563–2571
Table 3
˚
Bond lengths (A) and angles (8) for 3b
Mn(1)–C(2)
Mn(1)–C(3)
Mn(1)–P(2)
O(2)–C(2)
O(1)–C(1)
O(4)–H(2)
1.780(2)
1.836(2)
2.347(1)
1.151(3)
1.131(3)
0.76(3)
Mn(1)–C(1)
1.835(2)
2.075(2)
2.354(2)
1.133(3)
0.88(3)
Mn(1)–O(4)
Mn(1)–P(1)
O(3)–C(3)
O(4)–H(1)
C(2)–Mn(1)–C(1)
C(1)–Mn(1)–C(3)
C(1)–Mn(1)–O(4)
C(2)–Mn(1)–P(2)
C(3)–Mn(1)–P(2)
C(2)–Mn(1)–P(1)
C(3)–Mn(1)–P(1)
P(2)–Mn(1)–P(1)
Mn(1)–O(4)–H(2)
O(2)–C(2)–Mn(1)
O(1)–C(1)–Mn(1)
91.05(10)
92.81(10)
89.93(10)
94.90(7)
176.51(7)
88.70(7)
96.05(7)
83.73(3)
126(3)
C(2)–Mn(1)–C(3)
C(2)–Mn(1)–O(4)
C(3)–Mn(1)–O(4)
C(1)–Mn(1)–P(2)
O(4)–Mn(1)–P(2)
C(1)–Mn(1)–P(1)
O(4)–Mn(1)–P(1)
Mn(1)–O(4)–H(1)
H(1)–O(4)–H(2)
O(3)–C(3)–Mn(1)
88.57(10)
179.02(8)
91.37(9)
87.46(7)
85.15(6)
171.12(7)
90.33(6)
121(2)
101(3)
176.7(2)
177.0(2)
176.8(2)
Hydrogen bonding interactions
˚
H . . . F Distance (A)
2.67(4)
2.63(4)
2.03(4)
2.16(5)
Angle (8)
104(2)
113(3)
152(4)
154(4)
O(4)–H(1) . . . F(4)1
O(4)–H(2) . . . F(4)1
O(4)–H(2) . . . F(1)1
O(4)–H(1) . . . F(19)1
˚
˚
respectively. Selected bond distances and angles for 3a are
located in Table 2 and the selected distances and angles for
3b are found in Table 3. Aqua complex 3a has a Mn–O(4)
more than 0.002 A in 5a and 0.003 A in 5b. The bond
distances in the tetrazole ligands are similar and lie within
the relatively small range 1.323–1.340 A suggesting p-
delocalization throughout the distorted pentagonal rings
which are consistent with other tetrazolato structures
previously reported [23,24]. Complex 5b crystallizes with
a molecule of benzene in the crystal lattice.
˚
˚
distance of 2.115 A. The ionic lattice is held together by
hydrogen bonding between hydrogen atoms of the coordi-
nated aqua ligand and the F atoms of the BF4 anion with
˚
H...F separations ranging from 1.80–2.48 A. Aqua com-
˚
plex 3b has a Mn–O(4) distance of 2.075 A and crys-
tallized with one molecule of water in the lattice. The
coordinated aqua ligand in 3b hydrogen bonds with BF4
˚
with H...F separations ranging from 2.03–2.67 A. In
addition the coordinated aqua ligand hydrogen bonds with
the lattice water molecule via one of the H atoms
˚
(H(1)...O(1W)51.78 A). Similar hydrogen bonding has
been observed in other transition metal aqua complexes
with BF4 [14].
Ortep diagrams of the tetrazolato complexes 5a and 5b
are shown in Figs. 3 and 4 respectively. Selected bond
distances and angles for 5a are located in Table 4 and the
selected angles and distances for 5b are found in Table 5.
The 5-trifluoromethyltetrazolato ligand in 5a and 5b are
similar. The rings are bound to manganese through N(2).
This is consistent with a cycloaddition reaction involving
attachment of the g nitrogen of the original azides, 4a,b,
on the nitrile carbon directly leading to the observed
tetrazoles, 5a,b. In contrast, the previously prepared tri-
azole from the reaction of 4a with an acetylene, underwent
an isomerization of the triazole ligand [1]. This isomeriza-
tion does not occur with the tetrazolato complexes reported
herein. The heterocyclic rings in 5a and 5b are essentially
planar with no ring atoms deviating from the plane by
%4 %%%%4
Fig. 3. Ortep diagram of fac-Mn(CO)3(depe)(NN2C(CF3)N), 5a, indicat-
ing labeling scheme, 50% thermal ellipsoids, and single CF3 conforma-
tion.

T.M. Becker et al. / Polyhedron 18 (1999) 2563–2571
2569
The Ortep diagram of the triphenylphosphino complex
6a is shown in Fig. 5. Selected bond distances and angles
for 6a are found in Table 6.
Supplementary data
Crystallographic data (excluding structure factors) for
the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as
supplementary publication nos. CCDC-115189–CCDC-
115193. Copies of the data can be obtained free of charge
on application to CCDC, 12 Union Road, Cambridge
CB2, 1EZ, UK (Fax: 144(1223)336-033; E-mail:
deposit@ccdc.cam.ac.uk). Structure factors are available
upon request from the authors.
Acknowledgements
%4 %%%%4
Fig. 4. Ortep diagram of fac-Mn(CO)3(dppe)(NN2C(CF3)N), 5b, indicat-
ing labeling scheme, 50% thermal ellipsoids, and single CF3 conforma-
tion.
Data on the CCD was collected through the Ohio
Crystallographic Consortium, funded by the Ohio Board of
Regents 1995 Investment Fund (CAP–075) located at the
Table 4
˚
Bond lengths (A) and angles (8) for 5a
Mn–C(1)
Mn–C(3)
Mn–P(1)
1.782(2)
1.819(2)
2.317(1)
1.152(2)
1.138(2)
1.337(2)
1.332(2)
1.478(3)
1.262(7)
1.279(7)
1.346(6)
Mn–C(2)
Mn–N(2)
Mn–P(2)
O(2)–C(2)
N(1)–C(5)
N(2)–N(3)
N(4)–C(5)
C(6)–F(39)
C(6)–F(2)
C(6)–F(19)
1.815(2)
2.056(2)
2.321(1)
1.146(2)
1.323(2)
1.323(2)
1.323(2)
1.259(6)
1.277(5)
1.323(5)
O(1)–C(1)
O(3)–C(3)
N(1)–N(2)
N(3)–N(4)
C(5)–C(6)
C(6)–F(1)
C(6)–F(29)
C(6)–F(3)
C(1)–Mn–C(2)
C(2)–Mn–C(3)
C(2)–Mn–N(2)
C(1)–Mn–P(1)
C(3)–Mn–P(1)
C(1)–Mn–P(2)
C(3)–Mn–P(2)
P(1)–Mn–P(2)
N(3)–N(2)–N(1)
N(1)–N(2)–Mn
C(5)–N(4)–N(3)
O(2)–C(2)–Mn
N(4)–C(5)–N(1)
N(1)–C(5)–C(6)
F(39)–C(6)–F(29)
F(29)–C(6)–F(19)
F(2)–C(6)–F(3)
F(1)–C(6)–C(5)
F(29)–C(6)–C(5)
F(3)–C(6)–C(5)
90.95(9)
91.07(10)
88.62(8)
89.08(6)
92.13(7)
91.21(7)
176.28(7)
84.18(2)
110.38(14)
129.17(11)
105.1(2)
176.3(2)
112.8(2)
123.6(2)
106.5(6)
105.2(5)
102.5(4)
114.3(5)
112.6(5)
110.7(4)
C(1)–Mn–C(3)
C(1)–Mn–N(2)
C(3)–Mn–N(2)
C(2)–Mn–P(1)
N(2)–Mn–P(1)
C(2)–Mn–P(2)
N(2)–Mn–P(2)
C(5)–N(1)–N(2)
N(3)–N(2)–Mn
N(2)–N(3)–N(4)
O(1)–C(1)–Mn
O(3)–C(3)–Mn
N(4)–C(5)–C(6)
F(1)–C(6)–F(2)
F(39)–C(6)–F(19)
F(1)–C(6)–F(3)
F(39)–C(6)–C(5)
F(2)–C(6)–C(5)
F(19)–C(6)–C(5)
89.21(9)
179.04(7)
89.95(7)
176.80(7)
91.40(4)
92.62(7)
89.66(4)
103.5(2)
120.45(12)
108.2(2)
178.3(2)
176.2(2)
123.6(2)
109.4(5)
108.0(5)
103.6(6)
113.1(3)
115.0(3)
110.9(3)

2570
T.M. Becker et al. / Polyhedron 18 (1999) 2563–2571
Table 5
Table 6
˚
˚
Bond lengths (A) and angles (8) for 5b
Bond lengths (A) and angles (8) for 6a
Mn(1)–C(2)
Mn(1)–C(3)
Mn(1)–P(1)
O(1)–C(1)
O(3)–C(3)
N(1)–N(2)
N(3)–N(4)
C(5)–C(6)
C(6)–F(4)
C(6)–F(3)
C(6)–F(2)
1.801(3)
1.827(3)
2.325(1)
1.144(3)
1.142(3)
1.334(3)
1.340(3)
1.468(4)
1.271(6)
1.342(9)
1.368(8)
Mn(1)–C(1)
Mn(1)–N(2)
Mn(1)–P(2)
O(2)–C(2)
N(1)–C(5)
N(2)–N(3)
N(4)–C(5)
C(6)–F(1)
C(6)–F(5)
C(6)–F(6)
1.826(3)
2.054(2)
2.333(1)
1.150(3)
1.325(3)
1.328(3)
1.327(3)
1.257(7)
1.321(8)
1.354(9)
Mn(1)–C(1A)
Mn(1)–C(3A)
Mn(1)–P(2A)
O(1A)–C(1A)
O(3A)–C(3A)
1.816(4) Mn(1)–C(2A)
1.830(4)
2.380(1)
2.425(1)
1.149(4)
1.810(4) Mn(1)–P(1A)
2.373(1) Mn(1)–P(3A)
1.145(4) O(2A)–C(2A)
1.152(4)
Mn(2)–C(1B)
Mn(2)–C(3B)
Mn(2)–P(2B)
O(1B)–C(1B)
O(3B)–C(3B)
1.814(4) Mn(2)–C(2B)
1.813(4) Mn(2)–P(1B)
2.362(1) Mn(2)–P(3B)
1.149(5) O(2B)–C(2B)
1.148(5)
1.818(4)
2.358(1)
2.441(1)
1.166(5)
C(2)–Mn(1)–C(1)
C(1)–Mn(1)–C(3)
C(1)–Mn(1)–N(2)
C(2)–Mn(1)–P(1)
C(3)–Mn(1)–P(1)
C(2)–Mn(1)–P(2)
C(3)–Mn(1)–P(2)
P(1)–Mn(1)–P(2)
N(3)–N(2)–N(1)
N(1)–N(2)–Mn(1)
C(5)–N(4)–N(3)
N(1)–C(5)–C(6)
F(4)–C(6)–F(5)
F(4)–C(6)–F(6)
F(1)–C(6)–F(2)
F(1)–C(6)–C(5)
F(5)–C(6)–C(5)
F(6)–C(6)–C(5)
O(1)–C(1)–Mn(1)
O(3)–C(3)–Mn(1)
89.54(12)
93.14(12)
91.13(10)
91.03(8)
92.11(9)
89.54(8)
176.41(9)
84.62(4)
111.0(2)
127.0(2)
104.5(2)
123.7(2)
108.0(5)
110.5(5)
105.4(5)
115.3(4)
112.9(4)
110.8(5)
178.3(2)
176.9(3)
C(2)–Mn(1)–C(3)
C(2)–Mn(1)–N(2)
C(3)–Mn(1)–N(2)
C(1)–Mn(1)–P(1)
N(2)–Mn(1)–P(1)
C(1)–Mn(1)–P(2)
N(2)–Mn(1)–P(2)
C(5)–N(1)–N(2)
N(3)–N(2)–Mn(1)
N(2)–N(3)–N(4)
N(1)–C(5)–N(4)
N(4)–C(5)–C(6)
F(1)–C(6)–F(3)
F(5)–C(6)–F(6)
F(3)–C(6)–F(2)
F(4)–C(6)–C(5)
F(3)–C(6)–C(5)
F(2)–C(6)–C(5)
O(2)–C(2)–Mn(1)
89.04(12)
178.91(10)
90.07(10)
174.73(8)
88.38(6)
90.14(9)
91.31(6)
103.0(2)
122.0(2)
108.0(2)
113.6(2)
122.7(3)
108.1(6)
101.7(5)
99.3(5)
C(3A)–Mn(1)–C(1A)
C(1A)–Mn(1)–C(2A)
C(1A)–Mn(1)–P(2A)
87.5(2)
85.6(2)
C(3A)–Mn(1)–C(2A)
C(3A)–Mn(1)–P(2A)
90.9(2)
85.64(11)
88.43(11) C(2A)–Mn(1)–P(2A) 173.19(12)
C(3A)–Mn(1)–P(1A) 166.21(11) C(1A)–Mn(1)–P(1A)
83.80(11)
83.43(4)
C(2A)–Mn(1)–P(1A)
C(3A)–Mn(1)–P(3A)
C(2A)–Mn(1)–P(3A)
P(1A)–Mn(1)–P(3A)
99.07(12) P(2A)–Mn(1)–P(1A)
91.76(11) C(1A)–Mn(1)–P(3A) 169.83(11)
84.30(11) P(2A)–Mn(1)–P(3A) 101.64(4)
98.67(4)
C(3B)–Mn(2)–C(1B)
C(1B)–Mn(2)–C(2B)
C(1B)–Mn(2)–P(1B)
C(3B)–Mn(2)–P(2B)
85.3(2)
86.1(2)
C(3B)–Mn(2)–C(2B)
C(3B)–Mn(2)–P(1B) 172.12(13)
95.4(2)
87.03(14) C(2B)–Mn(2)–P(1B)
93.3(2)
86.0(2)
86.42(13)
84.35(4)
C(1B)–Mn(2)–P(2B)
P(1B)–Mn(2)–P(2B)
C(2B)–Mn(2)–P(2B) 168.1(2)
C(3B)–Mn(2)–P(3B)
C(2B)–Mn(2)–P(3B)
P(2B)–Mn(2)–P(3B)
88.58(13) C(1B)–Mn(2)–P(3B) 172.23(12)
89.72(13) P(1B)–Mn(2)–P(3B)
98.75(4)
112.4(4)
114.1(5)
113.2(4)
177.5(2)
99.19(4)
University of Toledo, Instrumentation Center in A&S,
Toledo, OH 43606.
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