Synthetic studies on the preparation of [Mn(CO)3{P(OR)3}{κ2-S,S′-Ph2P(S)NP(S)Ph2}], R?= Ph, Et

Article abstract of DOI:10.1016/j.jorganchem.2017.05.017

Complexes [Mn(CO)₃P(OR)₃{κ²-S,S′-Ph₂P(S)NP(S)Ph₂}], R = Ph, Et were prepared using four reaction routes. P(OPh)₃ presented similar electronic properties to CO in substitution reactions. Tri

Full text of DOI:10.1016/j.jorganchem.2017.05.017

Journal of Organometallic Chemistry 842 (2017) 59e66
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Journal of Organometallic Chemistry
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Synthetic studies on the preparation of [Mn(CO)3{P(OR)3}{k2-S,S0-
Ph2P(S)NP(S)Ph2}], R ¼ Ph, Et*
Liliana Capulín-Flores a, Othoniel Reyes-Camacho a, Marisol Reyes-Lezama a,
b
a, *
€
ꢀ
~
Herbert Hopfl , Noe Zúniga-Villarreal
a
ꢀ
ꢀ
ꢀ
Instituto de Química, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Circuito Exterior, 04510 Ciudad de Mexico, Mexico
Centro de Investigaciones Químicas, Universidad Autonoma del Estado de Morelos, Avenida Universidad 1001, C.P. 62210 Cuernavaca Morelos, Mexico
b
ꢀ
a r t i c l e i n f o
a b s t r a c t
Complexes [Mn(CO)3P(OR)3{k2-S,S0-Ph2P(S)NP(S)Ph2}], R ¼ Ph, Et were prepared using four reaction
routes. P(OPh)3 presented similar electronic properties to CO in substitution reactions. Tri-
organylphosphites turned out to be finer electronic tuners than triorganylphosphines in related carbonyl
complexes. The best route for preparation of each complex was dependent on the nature of the phos-
phite. Characterizations were achieved by IR, mass, NMR (1H, 13C, 31P) spectroscopies, and by single-
crystal X-ray diffraction.
Article history:
Received 26 January 2017
Received in revised form
4 May 2017
Accepted 6 May 2017
Available online 8 May 2017
© 2017 Elsevier B.V. All rights reserved.
Keywords:
Bromopentacarbonylmanganese
Triorganophosphites,
Dithioimidodiphosphinic acid
Carbonyl substitution reactions
1. Introduction
goes without saying that synthetic coordination and organome-
tallic chemistry will benefit from further studies on the coordina-
The complexes containing tetraphenylimidodichalcogenodi-
phosphinate ligands ([N(EPPh2)2]ˉ E ¼ O, S, Se, and Te) have
attracted wide attention in several areas of chemistry such as bio-
inorganic chemistry [1], homogeneous catalysis [2], material sci-
ences [3] to mention but a few. The coordination modes of these
ligands are accountable for the structure and reactivity that their
metal complexes exhibit [4] and; in this respect, we have been
investigating the chemistry of Mn and Re bromocarbonyls towards
the [N(EPR2)2]ˉ (E ¼ O, S, Se; R ¼ Me, Ph) anions and the reactivity of
the resulting carbonyl complexes with phosphines which possess
the ability to tune electron density at the metal center [5]. Phos-
phites are less sensitive to oxidation than phosphines displaying a
comparable capacity to tune electron density at the metal center
[6]; and their applications are not unknown, for example, in cata-
lytic processes: Hydroformylation of olefins with a rhodium tri-
phenyl phosphite complex is documented since the end of the 60's
[7]; and more recently, it was reported the intermolecular hydro-
amination of olefins by a triphenyl phosphite gold complex [8]. It
tion capabilities of the phosphites. In the present study we turned
our attention to assessing the coordination behavior of phosphites
P(OR)3, R ¼ Et, Ph vs [N(EPR2)2]ˉ towards [MnBr(CO)5].
2. Experimental
All preparative work was conducted in an atmosphere of dry
oxygen free nitrogen using conventional Schlenk techniques.
Toluene and cyclohexane were carefully dried and deoxygenated by
distillation from sodium benzophenone ketyl. Dichloromethane
was dried by distillation from phosphorus pentoxide. [MnBr(CO)5],
chlorodiphenylphosphine, hexamethyldisilazane, and potassium
tert-butoxide were acquired from Strem Chemicals, Co. and used
with no further purification except for the chlor-
odiphenylphosphine which was distilled under vacuum (102 ꢀC,
1 mmHg). Triphenyl and triethyl phosphite were acquired from
Sigma-Aldrich. Triethyl phosphite was distilled under vacuum.
Sulfur was from Fisher Reagents Scientific Company. K[N(SPPh2)2]
[9] and [Mn(CO)4{Ph2P(S)NP(S)Ph2-k
2S}] (a) [10] were prepared
according to literature procedures. IR spectra were obtained in so-
lution (4000e580 cmꢁ1) and in KBr disk (4000-200 cmꢁ1) using a
Bruker Alpha FT-IR spectrometer. 1H(300 MHz), 13C(75.6 MHz), and
31P(121.7 MHz) NMR spectra were recorded in chloroform-d,
*
In memory of Professor Erika Martin Arrieta.
* Corresponding author.
~
E-mail address: zuniga@unam.mx (N. Zúniga-Villarreal).
http://dx.doi.org/10.1016/j.jorganchem.2017.05.017
0022-328X/© 2017 Elsevier B.V. All rights reserved.

60
L. Capulín-Flores et al. / Journal of Organometallic Chemistry 842 (2017) 59e66
dichloromethane-d2 and bezene-d6 solutions at room temperature
using a Bruker Advance 300 instrument, unless otherwise stated.
Chemical shifts are reported in ppm relative to TMS (for 1H and 13C)
and H3PO4 (85% aqueous solution for 31P). FAB(þ) mass spectra were
recorded using a JEOL-SX 102A instrument with m-nitrobenzyl
alcohol as matrix. Melting points were determined on a Fisher-Johns
apparatus and are uncorrected. Reaction times were determined by
[MnBr(CO)5] (0.298 g, 1.08 mmol) was added to a round-bottom
flask, equipped with a stirring bar, containing 200 mL of cyclo-
hexane and heated to 50 ꢀC; an equimolar amount of the corre-
sponding phosphite (triphenyl phosphite 0.3 mL and triethyl
phosphite, 0.2 mL) was added. The reaction was left for 90 min and
after reaching room temperature, evaporation under vacuum
afforded an oily yellow material, complex (b), that was washed
with cold hexane (10 mL). The hexane was removed under reduced
pressure leaving behind complex (b) as an orange solid material. In
the case of complex (c), no isolation was effected due to decom-
position of the product and, as soon as complex (c) was detected as
the main product, the reaction was left at room temperature and
stored at 0 ꢀC; and the yield was calculated based on the amount of
complex (2) obtained in a further step (see below).
IR spectroscopy (monitoring of the n(CO) bands) and established as
the time when no further changes occurred in the spectra.
2.1. Procedures
2.1.1. Route A
Synthesis
of
[Mn(CO)3{P(OR)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}],
R ¼ Ph (1) and Et (2).
Complex (b): Yield: 0.559 g (93%); m.p. 74e76 ꢀC. nmax(C6H14)/
cmꢁ1 2100 m, 2034s, 2021vs,1976s (CO). 1H NMR (CDCl3, 300 MHz):
[Mn(CO)4{k2-S,S0-Ph2(S)NP(S)Ph2}] (a) (0.043 g, 0.07 mmol) was
added to a 250-mL round-bottom flask with stirring containing
100 mL of dry toluene. The temperature was set at 50 ꢀC. An
equimolar amount of the corresponding phosphite was added
d
/ppm: 7.3e7.2 [m, Hm], 7.2e7.1 [m, Ho and Hp]. 13C{1H} NMR (CDCl3,
75.6 MHz):
d
/ppm: 150.91 [d, Ci, 2JCi-P ¼ 11 Hz],129.97 [s, Cm],125.84
[s, Cp],121.22 [d, Co, 2JCo-P ¼ 5 Hz]. 31P{1H} NMR (CDCl3,121.7 MHz):
d/
(triphenyl phosphite 0.022 g, 19
m
L; triethyl phosphite 0.012 g,
ppm: 147.0 [s, broad]. MS (m/e): 556 [M]þ, 477 [M - Br]þ, 449 [M-
Br(CO)]þ, 444 [M-4(CO)]þ, 365 [M-Br4(CO)]þ. Anal. Calcd for
13 L) and after some time (30 min for triphenyl phosphite and
m
10 min for triethyl phosphite) the reaction finished and the heating
was withdrawn. The solvent was eliminated under reduced pres-
sure leaving an oily yellow product. A solid material was obtained
when cold dry hexane (15 mL) was added. Crystallization was
effected in a toluene/dichloromethane mixture at 4 ꢀC for several
days giving crystalline yellow powder.
C
22H15O7PBrMn: C, 47.44; H, 2.70%. Found: C, 47.29; H, 2.91%.
Complex (c): Yield: 0.11 g (25%); nmax(C6H14)/cmꢁ1 2094 m,
2030s, 2007vs, 1975s (CO). 31P{1H} NMR (CDCl3, 121.7 MHz):
ppm: 155.42 [s,{P(OEt)3}].
d/
2.1.2.1. [Mn(CO)3{P(OPh)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}] (1) from (b).
(0.1 g, 0.18 mmol) of [MnBr(CO)4P(OPh)3] (b) and an equimolar
amount of K[N(SPPh2)2] (0.088 g) were added to a round-bottom
flask containing 150 mL of dry toluene. The reaction mixture was
set at reflux temperature for 70 min; the heating was withdrawn
and the reaction mixture was left to reach room temperature and
passed through a sintered glass funnel containing Celite™. The
solvent was eliminated under reduced pressure giving an oily yel-
low material. 5 mL of cold hexane was added obtaining a yellow
powder. The solid was washed with ice cold hexane (3 ꢂ 5 mL) to
afford complex (1). Yield: 0.077 g (48%).
Complex (1): Yield: 0.038 g (61%); m.p. 114e116 ꢀC (dec.). nmax(-
ATR)/cmꢁ1 2020s, 1948s, 1915s (CO); 1212s nas(P2N); 569vs nas(PS);
515s ns(PS). nmax(CH2Cl2)/cmꢁ1 2031s, 1962s, 1928s (CO). 1H NMR
(CD2Cl2, 300 MHz): d/ppm: 8.1e7.9 [m, Ho and Ho’(PNP)], 7.5e7.2 [m,
aromatic protons: PNP and P(OPh3)]. 13C{1H} NMR (CD2Cl2,
2
75.6 MHz):
d
/ppm: 151.72 [d, Ci, {P(OPh)3}, JCi-P[P(OPh)3] ¼ 12 Hz],
138.63 [d, Ci’, (PNP), JCi’-P(PNP) ¼ 106 Hz], 137.48 [dd, Ci, (PNP), JCi-
¼ 114 Hz, 4JCi-P[P(OPh)3] ¼ 8 Hz], 131.15e130.47 [m, Cm and Cm’
P(PNP)
(PNP)], 129.63 [s, broad, Cp and Cp’ (PNP)], 129.58 [s, Cm {P(OPh)3}],
128.30e127.72 [m, Co and Co’ (PNP)], 124.87 [s, Cp {P(OPh)3}], 121.22
[d, Co {P(OPh)3}, JCo-[P(OPh)3] ¼ 4 Hz]. 31P{1H} NMR (CD2Cl2,
3
121.7 MHz):
d
/ppm: 173.7 [m, broad, {P(OPh)3}], 40.8 [d, (PNP) 3JPNP-
2.1.2.2. [Mn(CO)3{P(OEt)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}] (2) from (c).
Complex (c) [MnBr(CO)4{P(OEt)3}], dissolved in 180 mL of cyclo-
hexane previously stored at 0 ꢀC, was allowed to reach room
temperature in a 250-mL round-bottom flask with a magnetic
stirring bar and K[N(SPPh2)2] (0.283 g, 0.58 mmol) was added and
maintained under cyclohexane reflux for 3 h. The solution was left
to reach room temperature and passed through a sintered glass
funnel containing Celite™. The solvent was removed under
reduced pressure giving an oily yellow material. 15 mL of ice cold
hexane was added obtaining a yellow solid after evaporation under
reduced pressure. The compound was purified using a silica gel
column under an inert atmosphere. Complex (2) was obtained in
47% yield (0.2 g) based on K[N(SPPh2)2].
¼ 24 Hz]. MS (m/e): 897 [M]þ, 813 [M-3CO]þ, 503 [M-3(CO)
P(OPh)3
{P(OPh)3}]þ. Anal. Calcd for C45H35NO6P3S2Mn: C, 60.20; H, 3.9; N,
1.56; S, 7.13%. Found: C, 58.31; H, 4.02; N, 1.56; S, 6.89%.
Complex (2): Yield: 0.012 g (22%); m.p. 99e100 ꢀC (dec.).
nmax(CH2Cl2)/cmꢁ1 2024s, 1950s, 1917s (CO). 1H NMR (C6D5CD3,
300 MHz): d/ppm: 8.15e7.92 [m, Ho and Ho’(PNP)], 7.62e7.22 [m,
aromatic protons, PNP], 4.25 [6H, quintet, -OCH2CH3, 3JH-H ¼ 6 Hz,
3
3JH-P[P(OEt)3] ¼ 6 Hz], 1.16 [9H, t, -OCH2CH3, JH-H ¼ 6 Hz]. 13C{1H}
2
NMR (C6D5CD3, 75.6 MHz):
d
/ppm: 219.68 [d, Ceq, (CO), JC-
¼ 35 Hz], 214.91 [d, Cax, (CO), 2JC-P ¼ 63 Hz], 140.46 [d, Ci (PNP), JCi-
P
¼ 106 Hz], 139.39 [dd, Ci’, (PNP), JCi-P(PNP) ¼ 108 Hz, 4JCi-P[P(OEt)
P(PNP)
¼ 5 Hz], 131.89 [d, Cm (PNP), JCi-P(PNP) ¼ 11 Hz], 131.62[s, Cp (PNP)],
3]
131.05 [d, Cm’ (PNP), JCi-P(PNP) ¼ 11 Hz], 131.04 [s, Cp’ (PNP)],
2
130.88e128.1 [m, Co and Co’ (PNP)}], 62.52 [d, -OCH2CH3 JC-P[P(OEt)
2.1.3. Route C
¼ 6 Hz], 16.65 [d -OCH2CH3, JC-P[P(OEt)3] ¼ 5 Hz]. 31P{1H} NMR
2.1.3.1. mer,trans-[MnBr(CO)3{P(OPh)3}2] (d). Into a 200-mL round-
bottom flask, furnished with a stirring bar and 150 mL of dry
cyclohexane, were added 1.1 mmol (0.3 g) of [MnBr(CO)5] and
2.2 mmol (0.6 mL) of triphenyl phosphite. The reaction mixture was
set at reflux temperature and left for 90 min. The IR spectrum
showed bands at 2067w, 2050s, 1994s and 1949s cmꢁ1 indicating
the presence of both isomers fac/mer,trans in a rate roughly esti-
mated as 40/1, resp. The solvent was eliminated under reduced
pressure obtaining a yellow powder, which was washed with 10 mL
of cold hexane. After complex (d) was crystalized from a 1:1
mixture of CH2Cl2/hexane at 4 ꢀC for several days isomerization had
3
3]
(C6D5CD3, 121.7 MHz): d/ppm: 153.42 [m, broad, {P(OEt)3}], 36.45
[d, 3JPNP P[P(OEt)3]
-
¼ 27 Hz]. MS (m/e): 753 [M]þ, 669 [M-3CO]þ, 503
[M-3(CO){P(OEt)3}]þ. Anal. Calcd. for C33H35NO6P3S2Mn: C, 52.59;
H, 4.68; N, 1.86; S, 8.38%. Found: C, 52.86; H, 4.85; N, 1.74; S, 8.05%.
When the reaction for complex (2) was carried out in
dichloromethane for 10 min at room temperature using equimolar
amounts of the starting materials and an isolation procedure
identical to the one above mentioned, the yield was 72%.
2.1.2. Route B
[MnBr(CO)4{P(OR)3}], R ¼ Ph (b) and Et (c).
occurred to isomer mer,trans showing IR n(CO) bands in hexane at

L. Capulín-Flores et al. / Journal of Organometallic Chemistry 842 (2017) 59e66
61
2067w, 1994s and 1949s cmꢁ1. Yield: 0.75 g (82%), m.p. 161e163 ꢀC.
nmax(CH2Cl2)/cmꢁ1 2070w, 2000s, 1949s (CO). 1H NMR (CDCl3,
was left under toluene reflux for 4 h during which the IR
pattern did not change.
n
(CO)
300 MHz): d C
/ppm: 7.22e7.17 [m, Hm], 7.09e7.04 [m, Ho and Hp]. 13
{1H} NMR (CDCl3, 75.6 MHz):
d
/ppm: 151.50 [d, Ci, 2JCi-P[P(OPh)3] þ 4J
2.1.4. Route D ‘one-pot’
2.1.4.1. Synthesis of [Mn(CO)3{P(OR)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}],
R ¼ Ph (1) and Et (2). In a 200 mL round bottom flask with 150 mL
of dry toluene were added [MnBr(CO)5] (0.106 g, 0.38 mmol), an
¼ 11 Hz], 129.63 [s, Cm], 125.10 [s, Cp], 121.3 [s, Co]. 31P
Ci-P[P(OPh)3’]
{1H} NMR (CDCl3, 121.7 MHz):
d/ppm: 155.60 [s, broad]. MS (m/e):
840 [M]2þ, 838 [M]þ, 759 [M - Br]þ, 675 [M-3(CO)Br]þ, 365 [M-
3(CO)Br{P(OPh)3]þ. Anal. Calcd for C39H30O9P2BrMn: C, 55.81; H,
3.58%. Found: C, 55.40; H, 3.69%.
equimolar amount of phosphite (P(OPh)3, 0.1 mL,
r
¼ 1.184 g/mL
and P(OEt)3, 0.065 mL,
r
¼ 0.969 g/mL) and 0.186 g of K[N(SPPh2)2].
The reaction mixture was stirred and set at reflux temperature and
after some time (40 min for triphenyl phosphite and 30 min for
triethyl phosphite) the reaction finished and the heating was
withdrawn. The reaction was left to reach room temperature and
filtered using a sintered glass funnel containing Celite™. The sol-
vent was eliminated under reduced pressure leaving an oily
yellowish product. 5 mL of ice cold hexane was added and after
stirring for 20 min a yellow powder formed. Finally, the solid ma-
terial was filtered off and dried under vacuum. Complex (1): Yield:
0.14 g (40%); Complex (2): Yield 0.046 g (16%).
2.1.3.2. fac-[MnBr(CO)3{P(OEt)3}2] (e). To a 250-mL round-bottom
flask with 80 mL of dry cyclohexane were added 0.58 mmol
(0.160 g) of [MnBr(CO)5] and 1.166 mmol (0.2 mL) of triethyl
phosphite. The reaction mixture was heated to 55 ꢀC and stirred for
90 min. The solvent was eliminated under reduced pressure,
obtaining a yellow powder, which was dissolved in hexane and
purified using a silica gel column. Crystallization was effected in a
mixture of hexane/dichloromethane at 4 ꢀC for several days
yielding crystalline orange powder.
Complex (e): Yield 0.26 g (79%), m.p. 98e99 ꢀC. nmax(C6H12)/
2.2. Crystal data
cmꢁ1 2043s, 1968vs, 1935s (CO). 1H NMR (CDCl3, 300 MHz):
d/ppm:
4.20 [12H, m, -OCH2CH3], 1.36 [18H, t, -OCH2CH3, 3JH-H ¼ 6 Hz]. 13
C
X-ray diffraction data were collected on Bruker Smart Apex
{1H} NMR (CDCl3, 75.6 MHz):
d/ppm: 219.01 [s, Ceq, (CO)], 214.48
CCD diffractometer Mo K
a
(
l
¼ 0.7103 Å) [11] at 100 K. The
[m, Cax, (CO)], 61.85 [s, -OCH2CH3], 16.02 [s, -OCH2CH3]. 31P{1H}
structures were solved using direct methods and standard dif-
ference map techniques, and were refined by full-matrix last-
squares procedures on F2 and corrected for absorption with
SADABS (SAINT-NT) [12]. Structure solution refinement and data
output were carried out with the SHELXL-97 program package
[13]. Non-hydrogen atoms were refined anisotropically. C-H
hydrogen atoms were placed in geometrically calculated positions
using the riding model.
NMR (CDCl3, 121.7 MHz): d/ppm: 164.35 [s,{P(OEt)3}]. MS (m/e):
552 [M]þ, 466 [M-3CO]þ, 387 [M-Br3(CO)]þ, 300 [M-
{P(OEt)33(CO)}, 221 [M-Br{P(OEt)33(CO)]þAnal. Calcd for
C
15H30O9P2BrMn: C, 32.69; H, 5.49%. Found: C, 32.56; H, 5.41%.
2.1.3.3. [Mn(CO)3{P(OR)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}] R ¼ Ph, (1) from
(d) and R ¼ Et, (2) from (e). fac-[MnBr(CO)3{P(OR)3}2], R ¼ Ph
Suitable crystals of (1), (2), (d), and (e) were obtained from a
CH2Cl2/hexane 1:1 solution and (b) from hexane; all of them at 4 ꢀC
for several days. Data were collected on a Bruker Smart Apex CCD
diffractometer. The X-ray analysis of the poor-quality crystals, in the
case of complex (e), served only to establish atom connectivity.
See Table 1 for Crystal data of complexes (1) and (2) and
Tables SM1 and SM2 of the Supplementary Material for (b) and (d),
respectively.
0.12 mmol, 0.1 g, 85
mL; R ¼ Et, 0.12 mmol, 0.07 g, 72
mL was dis-
solved in 150 mL of dry toluene. An equimolar amount (0.058 g) of
K[N(SPPh2)2] was added. The reaction mixture was set to reflux
temperature for 95 min and the heat was withdrawn to allow the
mixture to reach room temperature. Then it was passed through a
sintered glass funnel which contained Celite™. The solvent was
eliminated under reduced pressure giving an oily-yellow material
which was dissolved in 5 mL of cold hexane and stirred for 30 min,
noticing the formation of a yellow solid. The solid was filtered and
washed with ice cold hexane (3 ꢂ 5 mL) and dried under vacuum.
Complex (1): Yield 0.066 g (61%). In the case of P(OEt)3 the reaction
2.2.1. [Mn(CO)3{P(OR)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}], R ¼ Ph (1), Et (2)
Table 1
Crystal data of (1) and (2).
(1)
(2)
Molecular formula
M
C45H35MnNO6P3S2
897.71
C33H35MnNO6P3S2
753.59
Temperature
Crystal size (mm)
Crystal system
Space group
a (Å)
100(2)K
298(2)K
0.48 ꢂ 0.42 x 0.35
0.41 ꢂ 0.37 x 0.22
Monoclinic
Triclinic
P21/c
20.749(3)
10.1326(16)
19.751(3)
90
95.818(3)
90
4131.1(11)
4
1.97e25.00
38902
P-1
9.38080(10)
12.02600(10)
17.2940(2)
94.1020(10)
92.0340(10)
110.6820(10)
1816.73(3)
b (Å)
c (Å)
a
b
g
(ꢀ)
(ꢀ)
(ꢀ)
V (Å3)
Z
2
q
Range for data collection (ꢀ)
1.817e25.348
17822
Reflections collected
Independent reflections
Goodness-of-fit on F2
Data/restraints/parameters
7280 (Rint ¼ 0.0457)
6631 (Rint ¼ 0.0224)
1.144
1.052
7280/0/523
6631/0/418
R1 ¼ 0.0341, wR2 ¼ 0.0885
R1 ¼ 0.0404, wR2 ¼ 0.0938
Final R indices [F2 > 2
s
(F2)]
R1 ¼ 0.0382, wR2 ¼ 0.0909
R indices (all data)
R1 ¼ 0.0399, wR2 ¼ 0.0920

62
L. Capulín-Flores et al. / Journal of Organometallic Chemistry 842 (2017) 59e66
3. Results and discussion
hand, when the reaction was effected in dichloromethane it took
10 min to completion at room temperature with a 72% yield. It is
apparent that solvent polarity plays a key role in this type of re-
action and solvent change brings about a change in reaction
mechanism. The carbonyl substitution regioselectivity was a result
of a mutually CO's trans effect to afford the corresponding fac
manganacycle carbonyls (1) and (2).
3.1. Syntheses
Complexes
[Mn(CO)3{P(OR)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}],
P(OR3) ¼ P(OPh)3 (1) and P(OEt)3 (2) were prepared by four routes
(A, B, C, and D) as shown in Scheme 1. Complexes (1) and (2) are
stable under a nitrogen atmosphere in the solid state at low tem-
perature for several months. Complex (2) decomposes at room
temperature in minutes in solution; while complex (1) resists
decomposition at the same conditions within hours. Both man-
ganacycles are soluble in organic solvents. Reactions were moni-
tored by IR spectroscopy and 31P{1H} NMR. The final reaction time
was determined when no further changes were observed in the
spectra.
3.1.2. Route B
3.1.2.1. Step iii. Our aim to prepare products (b) and (c) was to
assess their reactivity towards K[[N(SPPh2)2]. A couple of syntheses
of (b) have been previously reported: One consisted in the reaction
of [Mn2(CO)8{P(OPh)3}2] and Br2 [15]; and the other, in the reaction
of [MnBr(CO)5] with P(OPh)3 [16]; neither report informed about
the procedure details and characterization was accomplished solely
by IR spectroscopy. We chose to synthesize (b) according to the
latter procedure due to commercial availability of the starting
materials. Equimolar amounts of [MnBr(CO)5] and P(OPh)3 were
reacted in cyclohexane at 50 ꢀC for 90 min giving (b) in 93% (see
Experimental). IR monitoring of the reaction showed that
diphosphite complex (d) was present in small amounts even when
an excess of the manganese carbonyl precursor was used at lower
reaction temperatures. No separation of (d) was effected due to its
similar physical properties to (b).
3.1.1. Route A
The preparation of precursor (a), [Mn(CO)4{k2-S,S0-Ph2P(S)NP(S)
Ph2}], was effected according to the literature [10].
3.1.1.1. Step ii. The relative nucleophilicity of the tri-
organophosphites was reflected in the reaction times determined
by IR spectroscopy (10 min vs 30 min for triethyl vs triphenyl
phosphite in toluene at 55 ꢀC, resp.). Since it is well known that
most carbonyl compounds react by a dissociative mechanism [14],
it is noteworthy that complex (a) does not. Such behavior is a result
of the presence of [N(SPPh2)2] in (a)’s coordination sphere and has
been found in substitution reactions with trialkyl- and triar-
ylphosphines [5(a)]. When the reaction was carried out in boiling
cyclohexane the reaction time was 1.5 h, however, the yield was not
determined due to extensive decomposition of complex (2). The
low yield of (2) both in toluene and boiling cyclohexane, therefore,
may have stemmed from its thermal instability. In both cases the
reaction mixture reached a yellow color which eventually faded to
afford a dark brown precipitate, presumably MnO2. On the other
In the case of the triethyl phosphite analog, complex (c), the
same procedure as (b), i.e., starting from [MnBr(CO)5] and P(OEt)3,
was followed. At the end of the reaction (c) was the major product
(characterization of (c) by spectroscopies other than 31P{1H}-NMR
and IR was not successful due to is instability); attempts at isolating
(c) were unsuccessful though. No reaction intermediates were
observed by IR reaction monitoring of
Material SM3).
n(CO) bands (Supplementary
3.1.2.2. Step iv. The IR monitoring of formation of complex (1)
starting from (b), step (iv) of Scheme 1, is shown in Fig. 1.
Scheme 1. Reaction routes for the synthesis of [Mn(CO)3{P(OR)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}], R ¼ Ph (1) and Et (2).
(1). Route A: i, 1:1, r.t., THF, 6 h, 74%; ii, 1:1, 50 ꢀC, toluene, 30 min, 61%. Route B: iii, 1:1, 50 ꢀC, cyclohexane 90 min, 93%; iv, 1:1, toluene reflux, 70 min, 48%. Route C: v, 2:1
(P(OPh)3:MnBr(CO)5), cyclohexane reflux, 90 min, 82% (fac/mer,trans, 40/1, resp.); vi, 1:1, toluene reflux, 95 min, 61%. Route D: vii, 1:1:1, toluene reflux, 40 min, 40%.
(2). Route A: ii, 1:1, r.t., dichloromethane, 10 min, 72% (50 ꢀC, toluene, 10 min, 22%). Route B: iii, 1:1, 50 ꢀC, cyclohexane 90 min, 90%; iv, 1:1, cyclohexane reflux, 3 h, 47%. Route C: v,
2:1 P(OEt)3:MnBr(CO)5, 55 ꢀC, cyclohexane, 90 min, 79%. vi, 1:1, toluene reflux, 4 h, no reaction. Route D: vii, 1:1:1, toluene reflux, 30 min, 16%.

L. Capulín-Flores et al. / Journal of Organometallic Chemistry 842 (2017) 59e66
63
The tetracarbonyl complex [Mn(CO)4{k2-S,S0-Ph2P(S)NP(S)Ph2}]
(2088, 2017, 1994, 1953 cmꢁ1) (a) appears at 30 min and is present
till the end of the reaction as a minor product; its presence may be
justified by formation of complex (f) (not detected in the ir moni-
toring), depicted in Fig. 2, resulting from attack by K[N(SPPh2)2] to
[MnBr(CO)4{P(OPh)3}] (b): Once complex (f) is formed coordina-
tion of the other sulfur atom of the [N(SPPh2)2]ˉ ligand gives rise,
upon extrusion of triphenyl phosphite, to chelate complex (a) on
the one hand; and, on the other to complex (1) upon extrusion of a
carbonyl group. At the end of the reaction the main product was (1)
due to recoordination of P(OPh)3 and CO release.
When the reaction was carried out with complex (c) no
complex (a), [Mn(CO)4{k2-S,S0-Ph2P(S)NP(S)Ph2}], was detected.
Such behavior underlines the difference in steric (Tolman cone
angle P(OR)3, R ¼ Ph, 128ꢀ, R ¼ Et, 109ꢀ) and electronic (pKa
P(OR)3, R ¼ Ph, ꢁ2.0, R ¼ Et, 3.31) properties of the phosphites
used in the present work [17], being triphenyl phosphite closely
related to a CO group in its coordination behavior; while the
Fig. 2. Reactions of complex (f).
Fig. 1. Reaction monitoring of formation of complex (1).

64
L. Capulín-Flores et al. / Journal of Organometallic Chemistry 842 (2017) 59e66
triethyl phosphite binds stronger the metal center and thus
preventing the formation of the tetracarbonyl complex
[Mn(CO)4{k2-S,S0-Ph2P(S)NP(S)Ph2}] (a).
under the reaction conditions employed for preparation of complex
(1) showed no formation of complex (2) whatsoever, the spectrum
remaining unchanged for 4 h (not even fac to mer,trans trans-
formation was detected). Such lack of reactivity could be caused by
the higher electron density at the metal center of (e) (2043, 1968,
and 1935 cmꢁ1 in cyclohexane) compared to (d) (2050 1994, and
3.1.3. Route C
3.1.3.1. Step v. The similarity of the coordinating ability of P(OPh)3
and CO encouraged us to prepare diphosphite complexes (d) and
(e) and explore their reactivity towards K[N(SPPh2)2] to achieve (1)
and (2), for comparison purposes.
1949 cmꢁ1 in hexane) as inferred from their fac isomers' IR
n(CO)
bands.
3.1.4. Route D
Triphenyl phosphite and [MnBr(CO)5] were reacted in a 2:1 M
ratio, resp. under cyclohexane reflux for 90 min to give (d) in 85%
yield as a mixture of isomers fac/mer,trans being the latter in small
amounts (40:1 resp. as roughly determined by IR). Both isomers
have been reported and characterized by elemental analysis and IR
spectroscopy and proposed that the fac/mer,trans isomerization
takes place by way of a five coordinate intermediate [18]. The fac
isomer was reported to form at 37 ꢀC for 12 h; while, the mer,trans
isomer formed at 55e60 ꢀC for 16 h; both in chloroform and with a
molar ratio 5:1 Triphenyl phosphite/[MnBr(CO)5] resp.; in our
hands, isomer fac was the main reaction product and when it was
set at low temperature for several days it crystalized as the mer,-
trans isomer as determined by a single crystal X-ray analysis and IR
spectroscopy. Such solid-state isomerization has been observed in
[MnBr(CO)4PPh3] when rearranging from cis to trans isomer [15].
Complex fac-(e) was formed upon reaction of a 2:1 M ratio,
P(OEt)3/[MnBr(CO)5] resp., in cyclohexane at 55 ꢀC for 90 min and
isolated as a yellow material in 79% yield. IR monitoring showed
that after 90 min the fac isomer started to isomerize to the mer,trans
isomer and at 2.5 h isomerization reaches an equilibrium where the
fac isomer is still the major isomer. IR spectra of both fac and
mer,trans isomers of complex (e) have been reported and our data
match well [19].
The equimolar reaction of [MnBr(CO)5], K[N(SPPh2)2], and the
corresponding phosphite constituted one pot Route D. Both re-
actions were carried out in toluene at reflux temperature. In the
case of P(OPh)3, the reaction took 60 min to reach completion
giving complex (1), [Mn(CO)3{P(OPh)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}],
in 40% yield. IR reaction monitoring (Supplementary Material SM5)
showed that at 20 min monophosphine complex (b) started to
appear along with the tetracarbonyl complex (a). This shows that
both P(OPh)3 and K[N(SPPh2)2] are competing for [MnBr(CO)5]. At
35 min of heating, complex (1) was present along with complex (a).
It is apparent then that complex (1) is firstly form from reaction of
(b) and K[N(SPPh2)2]. At 45 min both complexes, (a) and (1),
reached an equilibrium where the latter was the major product. The
comparative nucleophilic power of K[N(SPPh2)2] and P(OPh)3
rendered Route D's yield low. Under same reaction conditions
[MnBr(CO)5], K[N(SPPh2)2], and triethyl phosphite formed complex
(2), [Mn(CO)3{P(OEt)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}], in 16% yield
within 30 min at toluene reflux temperature; IR monitoring of the
reaction showed no further changes upon longer heating. Such
poor yield may be accounted for by formation of complex (e) within
30 min at toluene reflux temperature which, as above mentioned,
was reluctant to further react with K[N(SPPh2)2].
The yields of the reaction Routes A e B are shown in Table 2 for
comparative purposes.
3.1.3.2. Step vi. When complex (d), freshly prepared, and
K
[N(SPPh2)2] were set to react under toluene reflux for 95 min
complex (1) was achieved in 61% yield. The reaction monitoring by
IR and 31P-{1H} NMR showed no extrusion of carbonyl group to
realize the bis(triphenyl phosphite) complex [Mn(CO)2{-
P(OPh)3}2{k2-S,S0-Ph2P(S)NP(S)Ph2}], but straightforward forma-
tion, upon triphenyl phosphite elimination, of final product
[Mn(CO)3{P(OPh)3}{k2-S,S0-Ph2P(S)NP(S)Ph2}] (1). No apparent
isomerization of fac to mer,trans isomer was detected by IR moni-
3.2. Infrared spectroscopy
The IR spectra of (1) and (2) are similar and show three bands in
CH2Cl2 solution in the n(CO) carbonyl region corresponding to the
2A’ þ A00 vibrational modes [20] arising from the carbonyl groups'
local symmetry with a Cs point group assigned to mononuclear
complexes with fac disposition involving both sulfur atoms [21].
The higher energy wavenumber corresponding to an A0 vibrational
mode (2031 and 2024 cmꢁ1 for complexes (1) and (2), resp.) reflects
toring of the
n(CO) bands (Supplementary Material SM4).
IR monitoring of reaction of complex (e) with K[N(SPPh2)2]
Table 2
Summary of Routes A e D for complexes (1) and (2).
Route
Complex
Step
Molar Ratio
Reaction conditions
Reaction time
Partial
Yield
(%)
Total
Yield
(%)
A
(1)
(2)
(1)
(2)
(1)
i
ii
i
ii
iii
iv
iii
iv
v
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
THF, r. t.
6 h
30 min
6 h
10 min
90 min
70 min
90 min
3 h
74.0
61.0
74.0
72.0
93.0
48.0
90.0
47.0
85.0
45.1
53.3
44.6
42.3
51.9
Toluene, 50 ꢀC
THF, r. t.
CH2Cl2, r. t.
B
C
Cyclohexane reflux
Toluene reflux
Cyclohexane reflux
Cyclohexane reflux
Cyclohexane reflux
2:1
90 min
P(OPh)3/MnBr(CO)5
vi
v
1:1
2:1
Toluene reflux
Cyclohexane 55C
95 min
90 min
61.0
79.0
(2)
_
P(OEt)3/MnBr(CO)5
vi
vii
vii
1:1
1:1:1
1:1:1
Toluene reflux
Toluene reflux
Toluene reflux
4 h
40 min
30 min
_
_
_
D
(1)
(2)
40.0
16.0

L. Capulín-Flores et al. / Journal of Organometallic Chemistry 842 (2017) 59e66
65
a stronger interaction of triethyl phosphite with the metal center
compared with triphenyl phosphite.
In previous work by us, the syntheses of complexes
[Re(CO)3(PR3){k2-S,S0-Ph2P(S)NP(S)Ph2}],
Ph, Me; among
others, were reported [5a]; their (CO) wave numbers together
a
R
¼
n
with those of complexes (1) and (2) are shown in Table 3.
The difference in wave number values between the phosphine
complexes is small (ca. 5 cmꢁ1) compared to the phosphite com-
plexes (7e12 cmꢁ1); such behavior points to a finer electronic
tuning at the metal center by the phosphites in the manganese
complexes; further studies are needed to find out if this holds true
for phosphites in the respective rhenium complexes or, for that
matter, in the respective phosphine complexes of manganese.
The IR spectra of complexes (b) [15], (d) [18], and (e) [19] have
been reported elsewhere and agree with ours. The IR spectrum of
Fig. 3. Magnetic inequivalence of the Ph groups in (1), R ¼ Ph and (2), R ¼ Et.
triplet’ with an apparent coupling constant of 6 Hz (Supplementary
Material SM9), although it might be expected to appear as a doublet
due to coupling to the adjacent phosphorus nucleus. Being a second
order spin system, the coupling constant can be broken down as 2J
þ
4J
¼ 11 Hz, where coupling is realized to
Ci-P[P(OPh)3]
Ci-P[P(OPh)3’]
(c) presents four bands in the n(CO) region in cyclohexane: 2094 m,
2030s, 2007vs, 1975s cmꢁ1 pointing to a C2v local symmetry arising
both trans positioned phosphite phosphorus nuclei [23]. As a
comparison, the 13C{1H} NMR spectrum of the monophosphite
complex (b) depicts at 150.91 ppm a doublet with a coupling
constant of 11 Hz assigned to the phenyl phosphite Ci (Supple-
mentary Material SM8).
from the 2A1 þ B1 þ B2 vibrational modes [22].
3.3. NMR spectroscopy
The 31P{1H} NMR spectra of complexes (1) and (2) show sym-
metrical coordination of the inorganic ligand [N(SPPh2)2]ˉ as evi-
denced by the appearance of a doublet at 40.8 ppm for (1) with a
coupling constant of 24 Hz and 36.45 ppm for (2) with a couple
3.4. Structural studies
The molecular structures of complexes (1) and (2) including
their atom numbering scheme are shown in Figs. 4 and 5, resp.
together with some selected bond distances and angles.
constant of 27 Hz. Both phosphine complexes [Re(CO)3(PR3){k2
-
S,S0-Ph2P(S)NP(S)Ph2}], R ¼ Ph, Me [5a] presented an [N(SPPh2)2]ˉ
31P{1H} NMR signal around 40 ppm (with coupling constants of 18
and 22 Hz, resp.). The 31P{1H} NMR chemical shifts of complexes (1)
and (2) concur with the observation made in the IR spectroscopy
section 3.2. that, in complexes (1) and (2), the phosphites make
finer electronic tuners than phosphines in their respective com-
plexes. The coordinated phosphites appear as a broad signal at
173.7 ppm for complex (1) and at 153.42 ppm for complex (2) (free
P(OPh)3 appears at 127.9 ppm and free P(OEt)3 at 133 ppm). 13C{1H}
NMR spectra of complexes (1) and (2) (Supplementary Material
SM6 and SM7, resp.) show two ipso carbon atoms Ci: 138.63 and
137.48 ppm for complex (1) and 140.46 and 139.39 ppm for com-
plex (2), resp. (see Experimental), indicating two inequivalent
phenyl rests on each phosphinoyl group, P]S(Ph2)(Ph)2P¼S, of the
[N(SPPh2)2]ˉ ligand. In complex (1) one Ci appears as a doublet with
a coupling constant of 106 Hz, while the other appears as a double
of doublets with two coupling constants, 114 and 8 Hz. Such cou-
plings arise from the spatial disposition of the phenyl groups of the
[N(SPPh2)2]ˉ ligand with respect to the coordinated phosphite: One
Ci couples to the phosphorus nucleus attached to it and to the
phosphorus nucleus of the phosphite located in a cisoid position (W
coupling), Fig. 3, while the other Ci couples only to the phosphorus
nucleus adjacent to it. The same situation presents in complex (2),
wherein the corresponding coupling constants amount to 106 Hz
for one Ci and 108 and 5 Hz for the other.
The molecular structures of complexes (b) and (d), their atom
numbering scheme, and some selected bond distances and angles
appear in the Supplementary Material (SM10 and SM11, resp.).
Structure similarity between complexes (1) and (2) warrants a
general discussion of their structural details. The dithioimidodi-
phosphinate effects a virtually symmetrical ligation to the man-
ganese center through both sulfur atoms (within experimental
error) rendering a six-membered ring manganacycle; the Mn-S
bond lengths are equivalent within experimental error indicating
covalent interactions (Scov(Mn,S) ¼ 2.44 Å) [24]. The phosphorus-
sulfur and phosphorus-nitrogen bond distances in the SPNPS
backbone are equivalent. They are longer and shorter, respectively,
than the corresponding bonds in free (S¼PPh2)2NH (cf. P-S (double
bond) 1.936(1), 1.950(1), P-N (single bond) av. 1.678(2) Å [25]. Their
magnitude is intermediate between single and double phosphorus-
The 13C{1H} NMR spectrum of diphosphite complex (d) shows
the mer,trans configuration found in the solid state (see Structrual
studies): the Ci of the triphenyl phosphite appears as a ‘virtual
Table 3
IR v(CO) bands of complexes (1), (2) and [Re(CO)3(PR3){k2-S,S0-Ph2P(S)NP(S)Ph2}],
R ¼ Ph, Me.
Fig. 4. Molecular structure of (1) with atom numbering scheme (ORTEP drawing with
50% probability ellipsoids, only ipso carbons shown on phosphorus triphenyl phos-
phite's and PNP's for clarity). Selected bond lengths [Å] and angles [ꢀ]; Mn(1)-S(1)
2.4108(7), Mn(1)-S(2) 2.4176(7), Mn(1)-C(1) 1.895(6), Mn(1)-C(2) 1.799(2), Mn(1)-
C(3) 1.790(2), Mn(1)-P(3) 2.2599(7), S(1)-P(1) 2.0130(8), P(1)-N(1) 1.588(2), P(2)-
N(1) 1.583(2); P(1)-N(1)-P(2)135.23(13), S(1)-Mn(1)-S(2) 91.94(2), S(1)-Mn(1)-S(2)
91.94(2), P(3)-Mn(1)-C(1) 174.95(7), C(3)-Mn(1)-S(1) 175.87(8), C(2)-Mn(1)-S(2)
170.69(7).
a
Complex
n
(CO)/cmꢁ1 bands in CH2Cl2
(1)
(2)
2031 1962 1928
2024 1950 1917
2023 1933 1899
2020 1928 1894
[Re(CO)3(PPh3){k2-S,S0-Ph2P(S)NP(S)Ph2}]
[Re(CO)3(PMe3){k2-S,S0-Ph2P(S)NP(S)Ph2}]
a
All bands' intensities are strong.

66
L. Capulín-Flores et al. / Journal of Organometallic Chemistry 842 (2017) 59e66
Road, Cambridge CB2 1EZ UK (Fax: þ44-1223-336-033; email:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Acknowledgements
ꢀ
The authors thank S. Hernandez-Ortega, L. M. Paz-Orta, L.
ꢀ
Velasco-Ibarra, and F. J. Perez-Flores for technical assistance
(Instituto de Química, UNAM). N. Z.-V. gratefully acknowledges
funding from CONACYT through grant 131329. L.C.F and O.R.C.
thank CONACyT for scholarships.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2017.05.017.
Fig. 5. Molecular structure of (2) with atom numbering scheme (ORTEP drawing with
50% probability ellipsoids only ipso carbons shown on phosphorus PNP's for clarity).
Selected bond lengths [Å] and angles [ꢀ]; Mn(1)-S(1) 2.4258(6), Mn(1)-S(2) 2.4200(6),
Mn(1)-C(1) 1.841(2), Mn(1)-C(2) 1.790(2), Mn(1)-C(3) 1.785(3), Mn(1)-P(3) 2.2878(6),
S(1)-P(1) 2.0131(7), P(1)-N(1) 1.590(2), P(2)-N(1) 1.588(2); P(1)-N(1)-P(2) 133.11(12),
S(1)-Mn(1)-S(2) 92.61(2), P(3)-Mn(1)-C(1) 176.46(7), C(3)-Mn(1)-S(1) 173.14(7), C(2)-
Mn(1)-S(2) 177.64(7).
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