Synthetic studies for the preparation of phosphorus carbonyl rhenacycles with the selenoimidodiphosphinate ligand [N(SePPh2)2]

Article abstract of DOI:10.1016/j.jorganchem.2006.12.028

The synthesis of the rhenacycles [Re(CO)₃(PR₃){Ph₂P(Se)NP(Se)Ph ₂-κ²Se}], PR₃ = PPh₃ (1), PMePh₂ (2), and PMe₂Ph (3) by a straightforward high yield procedure is described. Attempts at the preparation of the spiro [Re(CO)₂(Ph₂PCH₂CH₂PPh ₂-κ²P){Ph₂P(Se)NP(Se)Ph₂- κ²Se}] resulted in the formation of complexes [Re₂(CO)₆{Ph₂P(Se)NP(Se)Ph₂- κ²Se}₂(μ-Ph₂PCH₂ CH₂PPh₂)] (4) and [Re(CO)₃(Ph₂PCH₂CH₂PPh ₂-κ²P){Ph₂P(Se)NP(Se)Ph₂- κSe}] (5). All new inorganic rhenacycles 1-5 were characterized in solution and in solid state. The X-ray diffraction analysis of [Re(CO)₃PPh₃{Ph₂P(Se)NP(Se)Ph ₂-κ²Se}] showed that its MnSePNPSe ring conformation is sensitive to temperature.

Full text of DOI:10.1016/j.jorganchem.2006.12.028

Journal of Organometallic Chemistry 692 (2007) 1698–1707
www.elsevier.com/locate/jorganchem
Synthetic studies for the preparation of phosphorus carbonyl
rhenacycles with the selenoimidodiphosphinate ligand [N(SePPh2)2]
a
a
a
´
Lucila Marquez-Pallares , Jorge Pluma-Pluma , Marisol Reyes-Lezama ,
a
b
a,
*
´
´
´
˜
Marisol Guizado-Rodrıguez , Herbert Hopfl , Noe Zuniga-Villarreal
¨
¨
a
Instituto de Quı´mica, Universidad Nacional Auto´noma de Me´xico, Ciudad Universitaria, Circuito Exterior, 04510 Me´xico, D.F., Mexico
Centro de Investigaciones Quı´micas, Universidad Auto´noma del Estado de Morelos, Av. Universidad 1001, C.P. 62210 Cuernavaca Morelos, Mexico
b
Received 13 December 2006; received in revised form 23 December 2006; accepted 23 December 2006
Available online 9 January 2007
Abstract
The synthesis of the rhenacycles [Re(CO)3(PR3){Ph2P(Se)NP(Se)Ph2-j2Se}], PR3 = PPh3 (1), PMePh2 (2), and PMe2Ph (3) by a
straightforward high yield procedure is described. Attempts at the preparation of the spiro [Re(CO)2(Ph2PCH2CH2PPh2-
j2P){Ph2P(Se)NP(Se)Ph2-j2Se}] resulted in the formation of complexes [Re2(CO)6{Ph2P(Se)NP(Se)Ph2-j2Se}2(l-Ph2PCH2CH2PPh2)]
(4) and [Re(CO)3(Ph2PCH2CH2PPh2-j2P){Ph2P(Se)NP(Se)Ph2-jSe}] (5). All new inorganic rhenacycles 1–5 were characterized in solu-
tion and in solid state. The X-ray diffraction analysis of [Re(CO)3PPh3{Ph2P(Se)NP(Se)Ph2-j2Se}] showed that its MnSePNPSe ring
conformation is sensitive to temperature.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Rhenium(I) complexes; 77Se NMR; Carbonyl substitution reactions; Tetraphenyldiselenoimidodiphosphinato complexes; Tertiary phosphines;
Bis(diphenylphosphino)ethane
1. Introduction
[13a,13b], Co [14], Rh [2,12b,12c], Ir [12b,15], group 10:
Ni [16], Pd [2,12c,16,17], Pt [2,12c,16,17], and group 11:
Cu [14,18a] Ag [18a,18b,18c] Au [18b,18d,18e]) to rare-
earth metals: Y [19], La, Gd, Er, Yb [20], and Sm [21].
Our interest in the structure and reaction chemistry of
the [N(EPPh2)2]ꢀ (E = O, S, Se) anions with carbonyl
complexes of Mn and Re led us to undertake a systematic
study thereof [22,11a,11c]. Recently, we reported the syn-
thesis of the [Mn(CO)4ꢀx(L)x{Ph2P(Se)NP(Se)Ph2-j2Se}]
complexes, where X = 1 for L = PPh3, and PMePh2; and
X = 2, for L = Ph2PCH2CH2PPh2 by two methods [11a].
In the present paper, we describe the synthesis of the rhe-
nacycles [Re(CO)3(PR3){Ph2P(Se)NP(Se)Ph2-j2Se}], PR3 =
PPh3 (1), PMePh2 (2), and PMe2Ph (3), using a different
method from those employed for the manganese analogs.
When the new method was tested to prepare the spiro
The coordination of the [N(EPPh2)2]ꢀ (E = O, S, Se)
anions has been widely studied over the last years. Their
potential applications in a number of fields (e.g. catalysis,
metal extraction studies, optoelectronics, NMR shift
reagents, to mention but a few) and their capability of
joining the metal center in different fashions and, at the
same time, adopting several ring conformations in inor-
ganic metallacycles have been two major reasons for their
extensive exploration [1]. As far as the coordination chem-
istry of the [N(SePPh2)2] fragment is concerned it has
been found that it binds a wide range of atoms: from
main group elements (K [2], group 12 [3]; Al and Ga
[4], In [5a,5b], Sn [3,6], Pb [3], Sb [5b,7], Bi [5b,7], Se
[8] and Te [9]), transition metals (V and Cr [10], Mn
[11a,11b,11c] and Re [11d,11e], Ru [12a,12b,12c], Os
compound
[Re(CO)2(Ph2PCH2CH2PPh2 j2P){Ph2P(Se)
NP(Se)Ph2-j2Se}] (whose Mn analog is known [11a])
complexes 4, [Re2(CO)6{Ph2P(Se)NP(Se)Ph2-j2Se}2 (l-
Ph2PCH2CH2PPh2)], and 5, [Re(CO)3(Ph2PCH2CH2-
*
Corresponding author. Fax: +52 56 16 22 03.
E-mail address: zuniga@servidor.unam.mx (N. Zu´niga-Villarreal).
˜
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.12.028

L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
1699
PPh2-j2P){Ph2P(Se)NP(Se)Ph2-jSe}] were obtained. All
new inorganic rhenacycles 1–5 were characterized in solu-
tion and in solid state.
745 w cmꢀ1; m(PSe) 538m cmꢀ1. IR (CH2Cl2): m(CO)
2020s, 1932 m, 1895m cmꢀ1
.
1H NMR (CDCl3,
3
300 MHz): d/ ppm: 8.05 [ddd, Ho(PNP), JH –P ¼ 6 Hz,
o
3
3JH –H ¼ 4 Hz, JH –H ¼ 2 Hz]; 7.22 [dt, Hp(PNP),
o
m
o
p
4
2. Experimental
3JH –H ¼ 7 Hz, JH –H ¼ 2 Hz]; 7.09 [dt, Hm(PNP),
p
m
p
o
3
4
3JH
¼ 7 Hz, JH
¼ 4 Hz, JH ¼ 4 Hz]; 7.48–7.34
m–Hp
m–Ho
m–P
All preparative work was effected in an atmosphere of
dry oxygen free nitrogen, using conventional Schlenk tech-
niques. Solvents were carefully dried; tetrahydrofuran,
ethyl ether, toluene, and hexane were dried and deoxygen-
ated by distillation from sodium benzophenone ketyl.
[ReBr(CO)5], chlorodiphenylphosphine, hexamethyldisilaz-
ane, and potassium tert-butoxide were acquired from Strem
Chemicals, Co. and used with no further purification except
for the chlorodiphenylphosphine, which was distilled under
vacuum (102 ꢁC, 1 mm Hg). Methyldiphenylphosphine, tri-
phenylphospine, dimethylphenylphosphine, and 1,2-
bis(diphenylphosphine)ethane were from Aldrich, Co. Gray
selenium was from Fisher Reagents Scientific Company.
HN(PPh2)2 [23], HN(SePPh2)2 [17], [K{(SePPh2)2N}] [2],
and [Re(CO)4{Ph2P(Se)NP(Se)Ph2-j2Se}] [11c] were pre-
pared according to the literature procedures. IR spectra
were obtained in solution (4000–580 cmꢀ1) and in KBr disk
(4000–200 cmꢀ1) using a Bruker Tensor 27 FT-IR spec-
trometer. 1H (300 MHz), 13C (75.57 MHz), 31P (121.67
MHz), and 77Se (57.34 MHz) NMR spectra were recorded
in chloroform-d solutions at room temperature using a Jeol
GX300 instrument. The chemical shifts are reported in ppm
[m, aromatic protons PPh3]. 13C NMR{1H} (CDCl3,
75.6 MHz): d/ppm: 137.10 [dd, Cipso (PNP), JC
¼
ipso–P
107 Hz, 3JC
¼ 10 Hz]; 127.65 [d, Co (PNP),
ipso–P
3JC –P ¼ 13 Hz]; 131.40 [d, Cm (PNP), 4JC ¼ 13 Hz];
m–P
o
130.5 [s, Cp (PNP)]; 137.70 [d, Cipso (PPh ), JC
¼
ipso–P
3
3
92 Hz]; 128.30 [d, Co (PPh3), JC –P ¼ 10 Hz]; 134.30 [d,
o
4
Cm (PPh ), JC ¼ 10 Hz]; 130.20 [s, Cp (PPh3)]; 190.50
m–P
3
[s, broad, C 2(CO) trans to SePNPSe]; 189.75 [s, broad,
C
(CO) trans to PPh3]. 31P NMR{1H} (CDCl3,
3
121.7 MHz): d/ppm: 28.62 [d, (PNP), JPNP–PPh ¼ 18 Hz,
3
JP–Se = 559 Hz
(satellites)];
9.50
[t,
(PPh3),
3JPNP–PPh ¼ 18 Hz]. 77Se NMR{1H} (CDCl3, 57.3 MHz):
3
1
2
d/ppm: ꢀ276.45 [dd, JPNP–Se = 559 Hz, JPPh –Se
¼
3
30 Hz]. MS (m/e): 1074 [M]+; 1018 [Mꢀ2(CO)]+; 913
[Mꢀ3(CO)ꢀ(Ph)]+.
2.1.1.2. [Re(CO)3(PMePh2){Ph2P(Se)NP(Se)Ph2-j2Se}]
(2). 0.32 g (0.56 mmol) of K[N(SePPh2)2], 0.23 g
(0.55 mmol) of [ReBr(CO)5], and 0.11 g (0.56 mmol) of
PMePh2.
0.54 g, 0.54 mmol 97% yield; M.p. 205–209 ꢁC. IR
(KBr): m(CO) 2015s, 1924s, 1896s cmꢀ1; m(P2N) 1178w,
744 w cmꢀ1; m(PSe) 538m cmꢀ1. IR (CH2Cl2): m(CO)
1
relative to TMS (for H and 13C), H3PO4 (85% aqueous
solution for 31P), and Ph2Se2/CDCl3 (set to 463.5 ppm for
77Se), respectively. FAB(+) mass spectra were recorded
using a JEOL SX-102A instrument with m-nitrobenzyl
alcohol as matrix in all cases. The melting points were deter-
mined on a Fisher–Johns apparatus and are uncorrected.
2022s, 1933m, 1898m cmꢀ1
.
1H NMR (CDCl3,
3
300.5 MHz): d/ppm: 8.07 [ddd, Ho(PNP), JH –P ¼ 7 Hz,
o
3
3JH –H ¼ 4 Hz, JH –H ¼ 2 Hz]; 7.26 [dt, Hp(PNP),
o
m
o
p
4
3JH –H ¼ 8 Hz, JH –H ¼ 2 Hz]; 7.14 [dt, Hm(PNP),
p
m
p
o
3JH
¼ 8 Hz, JH
¼ 4 Hz, JH ¼ 4 Hz]; 7.41–7.65
3
4
m–Hp
m–Ho
m–P
[m, aromatic protons PMePh2]; 2.33 [d, Me(PMePh2),
2.1. General procedures
2JH–P = 8 Hz]. 13C NMR{1H} (CDCl3, 75.6 MHz): d/
3
ppm: 136.90 [dd, Cipso (PNP), JC
¼ 107 Hz, JC
¼
ipso–P
ipso–P
2.1.1. Method A
3
9 Hz]; 127.80 [d, Co (PNP), JC –P ¼ 14 Hz]; 131.40 [d, Cm
Synthesis of [Re(CO)3(PR3){Ph2P(Se)NP(Se)Ph2-j2Se}]
complexes for PR3 = PPh3 (1); PMePh2 (2); and PMe2Ph
(3).
o
4
(PNP), JC ¼ 12 Hz]; 130.00 [s, Cp (PNP)]; 138.00 [d,
m–P
Cipso (PMePh ), JC
¼ 94 Hz]; 128.43 [d, Co (PMePh2),
ipso–P
2
3JC –P ¼ 10 Hz]; 132.43 [d, Cm (PMePh ), JC ¼ 10 Hz];
4
m–P
2
o
K[N(SePPh2)2], [ReBr(CO)5], and PR3 (for quantities
see below) were added to a 100 mL round bottom flask
containing 70 mL of dry toluene. After some time under
reflux (30 min for 1, 1 h for 2, and 1 h 15 min for 3) the sol-
vent was eliminated under reduced pressure leaving an off-
white material. The product was washed with dry hexane
(2 · 15 mL) and dissolved in dichloromethane to filter off
KBr. Crystallization was effected in a mixture of hexane/
dichloromethane at 4 ꢁC for several days yielding crystal-
line powders in the three cases.
130.60 [s, Cp (PMePh2)]; 134.90 [d, Cipso (PMePh2),
3
JC
¼ 44 Hz]; 128.30 [d, Co (PMePh2), JC –P ¼ 16 Hz];
ipso–P
o
130.80 [d, Cm (PMePh2), 4JC ¼ 11 Hz], 131.20 [s, C
m–P
p
(PMePh )]; 15.5 [d, JC
¼ 31 Hz]; 190.23 [d, C 2(CO),
Me–P
2
2Jcis(C–P) = 8 Hz]; 189.75 [d, C (CO), 2Jtrans(C–P) = 8 Hz].
31P NMR{1H} (CDCl3, 121.7 MHz): d/ppm: 27.94 [d,
3
(PNP), JPNP–PPh ¼ 18 Hz, JP–Se = 560 Hz (satellites)];
3
ꢀ12.10 [t, (PMePh2), JPNP–PPh ¼ 20 Hz]. 77Se NMR
3
3
{1H} (CDCl3, 57.3 MHz): d/ppm: ꢀ289.35 [dd,
1JPNP–Se ¼ 560 Hz, JPMePh -Se ¼ 34Hz]. MS (m/e): 1013
2
2
[M]+, 985 [MꢀCO]+; 957 [Mꢀ2(CO)]+; 929 [Mꢀ3(CO)]+;
2.1.1.1. [Re(CO)3(PPh3){Ph2P(Se)NP(Se)Ph2-j2Se}]
(1). 0.58 g (0.8 mmol) of K[N(SePPh2)2], 0.4 g (0.99
mmol) of [ReBr(CO)5], and 0.26 g (1.00 mmol) of PPh3.
1.04 g, 0.96 mmol 98% yield; M.p. 213–215 ꢁC. IR
(KBr): m(CO) 2017s, 1928s, 1891s cmꢀ1; m(P2N) 1179w,
852 [Mꢀ3(CO)ꢀ(Ph)]+; 729 [Mꢀ3(CO)ꢀ(PMePh2)]+.
2.1.1.3. [Re(CO)3(PMe2Ph){Ph2P(Se)NP(Se)Ph2-j2Se}]
(3). 0.58 g (0.8 mmol) of K[N(SePPh2)2], 0.35 g

1700
L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
(0.86 mmol) of [ReBr(CO)5], and 0.12 g (0.86 mmol) of
PMe2Ph.
Synthesis of [Re2(CO)6{Ph2P(Se)NP(Se)Ph2-j2Se}2-
(l-Ph2PCH2CH2PPh2)] (4)
0.57 g, 0.6 mmol 70% yield; M.p. 165–170 ꢁC. IR (KBr):
m(CO) 2013s, 1918s, 1887s cmꢀ1; m(P2N) 1176w, 743w
cmꢀ1; m(PSe) 539m cmꢀ1. IR (CH2Cl2): m(CO) 2019s,
In a 100 mL round bottom flask with 70 mL of dry tol-
uene K[N(SePPh2)2] was added (0.2 g, 0.34 mmol) with
0.14 g (0.33 mmol) of [ReBr(CO)5]; the reaction mixture
was stirred and set at 82–85 ꢁC. The reaction was carefully
monitored by IR spectroscopy. Once the complex
[Re(CO)4{Ph2P(Se)NP(Se)Ph2-j2Se}] was detected as the
only product (20 min) the reaction was allowed to stand
at room temperature (25 ꢁC) for around 10 min. An equi-
molar amount of Ph2PCH2CH2PPh2 was added to the
reaction mixture and set to toluene reflux temperature for
5 h. An off-white powder was obtained after the solvent
was taken away under reduced pressure. Addition of
25 mL of dichloromethane allowed removal of KBr by fil-
tration. The solvent was reduced under vacuum and crys-
tallization from a mixture of hexane/dichloromethane
afforded complex 4 in 70% yield and m.p. 200–205 ꢁC. IR
(KBr): m(CO) 2017s, 1929s, 1895s cmꢀ1; m(P2N) 1181w,
744w cmꢀ1; m(PSe) 539m cmꢀ1. IR (CHCl3): m(CO) 2020s,
1
1929m, 1895m cmꢀ1. H NMR (CDCl3, 300.5 MHz): d/
3
3
ppm: 8.06 [ddd, Ho(PNP), JH –P ¼ 8 Hz, JH –H ¼ 7 Hz,
o
o
m
3JH –H ¼ 2 Hz]; 7.30 [dt, Hp(PNP), JH –H ¼ 8 Hz,
3
o
p
p
m
4JH –H ¼ 2 Hz]; 7.20 [dt, Hm(PNP), 3JH
¼ 8 Hz,
m–Hp
p
o
3JH
¼ 7 Hz, 4JH ¼ 2 Hz]; 7.38–7.60 [m, aromatic
m–Ho
m–P
2
protons PMe2Ph]; 2.33 [d, Me(PMe2Ph), JH–P = 8 Hz];
1.76 [dd, Me(PMe2Ph), JH–P = 8 Hz, JH–H = 25 Hz]. 13C
2
2
NMR{1H} (CDCl3, 75.6 MHz): d/ppm: 136.90 [dd, Cipso
(PNP), JC
¼ 105 Hz, 3JC
¼ 8 Hz]; 127.90 [d,
ipso–P
ipso–P
Co(PNP), 3JC –P ¼ 14 Hz]; 131.40 [d, Cm (PNP),
o
4JC ¼ 13 Hz]; 129.66 [s, Cp (PNP)]; 138.2 [d, Cipso
m–P
(PMe Ph), JC
¼ 97 Hz]; 128.24 [d, C (PMe2Ph),
ipso–P
2
o
3JC –P ¼ 14 Hz]; 130.74 [d, Cm (PMe Ph), JC ¼ 12 Hz];
4
m–P
2
o
131.20 [s, C (PMe Ph)]; 15.20 [d, Me (PMe Ph), JC
¼
Me–P
p
2
2
2
31 Hz]; 189.93 [d, C 2(CO), Jcis(C–P) = 8 Hz]; 190.17 [d,
C (CO), 2Jtrans(C–P) = 8 Hz]. 31P NMR{1H} (CDCl3,
1936 m, 1904m cmꢀ1 1H NMR (CDCl3, 300 MHz): d/
.
3
3
3
121.7 MHz): d/ppm: 27.56 [d, (PNP), JPNP–PPh ¼ 21 Hz,
ppm: 7.90 [ddd, Ho(PNP), JH –P ¼ 7 Hz, JH –H ¼ 3 Hz,
3
o p p m
o
o
m
3
JP–Se = 562 Hz (satellites)]; ꢀ30.22 [t, (PMePh2),
3JH –H ¼ 2 Hz]; 7.10 [dt, Hm(PNP), JH –H ¼ 7 Hz,
3JPNP–PPh ¼ 21 Hz]. 77Se NMR{1H} (CDCl3, 57.3 MHz):
4JH –H ¼ 3 Hz]; 7.43–7.32 [m, aromatic protons Ph2PCH2-
p
o
3
1
2
d/ppm: ꢀ298.25 [dd, JPNP–Se = 562 Hz, JPMePh –Se
¼
CH2PPh2 and Hp of PNP]; 2.70 [dd, HPh PCH CH PPh ,
2 2 2 2
2
36 Hz]. MS (m/e): 951 [M]+; 895 [Mꢀ2(CO)]+; 867
[Mꢀ3(CO)]+; 790 [Mꢀ3(CO)ꢀ(Ph)]+; 729 [Mꢀ3(CO)ꢀ
(PMePh2)]+.
3JH–H ¼ 8 Hz, 3JH–H ¼ 12 Hz]. 13C NMR{1H} (CDCl3,
cis
trans
75.6 MHz):
d/ppm:
133.50
[d,
Cipso
3
(PNP),
JC
¼ 90 Hz]; 128.10 [d, C (PNP), JC –P ¼ 15 Hz];
ipso–P
o
o
133.30 [d, Cm (PNP), 4JC ¼ 11 Hz]; 131.10 [s, Cp
m–P
2.1.1.4. Reaction of K[N(SePPh2)2], [ReBr(CO)5], and
Ph2PCH2CH2PPh2. K[N(SePPh2)2] (0.2 g, 0.34 mmol),
[ReBr(CO)5] (0.14 g, 0.34 mmol) and Ph2PCH2CH2PPh2
(0.14 g, 0.34 mmol) were added to a 100 mL round bottom
flask containing 70 mL of dry toluene. After 5 h under reflux
the solvent was removed under reduced pressure leaving an
off-white material. The product was washed with dry hexane
(2 · 15 mL) and dissolved in dichloromethane to filter off
KBr. Complexes 4 and 5 were obtained as a mixture being
the latter the major product. Both 4 and 5 could be obtained,
independently, as main products by Method B (see below).
(PNP)]; 133.40 [d, Cipso (Ph PCH CH PPh ), JC
¼
ipso–P
2
2
2
2
3
45 Hz]; 127.60 [d, Co (Ph2PCH2CH2PPh2), JC –P ¼ 14
o
Hz]; 131.40 [d, Cm Ph2PCH2CH2PPh2, 4JC ¼ 11 Hz];
m–P
130.90 [s, Cp (Ph2PCH2CH2PPh2)]. 31P NMR{1H} (CDCl3,
121.7 MHz): d/ppm: 28.30 [d, (PNP), 3JPNP–Ph PCH CH PPh
¼
2
2
2
2
21 Hz]; 3.10 [broad s (linewidth = 48 Hz), (Ph2PCH2CH2-
PPh2)].
Complex [Re(CO)3(Ph2PCH2CH2PPh2-j2P){Ph2P(Se)
NP(Se)Ph2-jSe}] (5), was obtained in the same manner
as 4 with half equimolar amount of added phosphine
(0.07 g, 0.17 mmol) and a shorter reflux time (30 min). 5
was isolated in 50% yield; M.p. 207–210 ꢁC. IR (KBr):
m(CO) 2024s, 1949s, 1912s cmꢀ1; m(P2N) 1181w, 739 w
cmꢀ1; m(PSe) 536m cmꢀ1. IR (CHCl3): m(CO) 2035s,
2.1.2. Method B
In a 100 mL round bottom flask with 70 mL of dry tol-
uene K[N(SePPh2)2] was added (0.58 g, 0.8 mmol) with
0.41 g (1.0 mmol) of [ReBr(CO)5]; the reaction mixture
was stirred and set to reflux temperature. The reaction
was carefully monitored by IR spectroscopy. Once the
complex was detected as the only product (20 min) the
reaction was allowed to stand at room temperature
(25 ꢁC) for around 10 min. PPh3 (0.18 g, 0.7 mmol) was
added to the reaction mixture and set to toluene reflux tem-
perature for 1.5 h. The solvent was evaporated to dryness
under reduced pressure leaving a whitish powder. Addition
of 25 mL of dichloromethane allowed separation of KBr
by filtration. The solvent was reduced under vacuum and
crystallization from a mixture of hexane/dichloromethane
afforded complex 1 in 90% yield (0.67 g, 0.62 mmol).
1
1964 m, 1918 m cmꢀ1. H NMR (CDCl3, 300 MHz): d/
3
3
ppm: 7.80 [ddd, Ho(PNPcoord.), JH –H ¼ 7 Hz, JH –P
¼
o
m
o
3 Hz, 3JH –H ¼ 2 Hz]; 7.60 [ddd, Ho(PNPdecoord.),
o
p
3
3
3JH –H ¼ 13 Hz, JH –P ¼ 4 Hz, JH –H ¼ 2 Hz]; 7.1 [dt,
o
m
o
o
p
Hm(PNP), 3JH
¼ 7 Hz, 3JH
¼ 7 Hz, 4JH
¼
m–Hp
m–Ho
m–P
3 Hz]; 7.55–7.15 [m, aromatic protons Ph2PCH2CH2PPh2].
13C NMR{1H} (CDCl3, 75.6 MHz): d/ppm: 136.00 [d, Cipso
(PNPcoord.), JC
¼ 90 Hz]; 127.30 [d, Co (PNPcoord.),
ipso–P
3JC –P ¼ 10 Hz];
132.40
[d,
Cm
(PNPcoord.),
o
4JC ¼ 12 Hz]; 130.40 [s, Cp (PNPcoord.)]; 141.20 [d, Cipso
m–P
(PNPdecoord.), JC
¼ 96 Hz]; 128.70 [d, Co (PNPdecoord.),
m–P
ipso–P
3JC –P ¼10Hz]; 132.80 [d, Cm (PNPdecoord.), 4JC ¼12Hz];
o
130.80 [s, Cp (PNPdecoord.)]; 133.60 [d, Cipso (Ph2PCH2CH2-
PPh ), JC
¼ 46 Hz]; 127.20 [d, C (Ph PCH CH PPh ),
ipso–P
2
o
2
2
2
2

L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
1701
3JC –P ¼ 4 Hz]; 131.90 [d, Cm (Ph2PCH2CH2PPh2),
full-matrix least-squares refinement. The structures were
solved by direct methods. All non-hydrogen atoms were
refined anisotropically. The residual electron densities from
a final difference Fourier synthesis were in the ranges of
1.994, ꢀ1.233 for 1; 1.935, ꢀ0.923 for 1a; 2.345, ꢀ1.658
for 2; 1.93ꢀ5,3 ꢀ0.923 for 3; 1.207, ꢀ1453 for 4; and 2.708,
o
4JC ¼ 11 Hz], 129.10 [s, Cp (Ph2-PCH2CH2PPh2)];
m–P
2
191.23 [d, C (CO), Jtrans(C–P) = 9 Hz]; 190.46 [d, C (CO),
2Jtrans(C–P) = 9 Hz]; 188.45 [d, C (CO), 2Jcis(C–P) = 7 Hz].
31P NMR{1H} (CDCl3, 121.7 MHz): d/ppm: 32.80
3
[d, (PNPdecoord.), JPNP–Ph PCH CH PPh ¼ 17 Hz]; 26.10 [d,
2
2
2
2
3
˚
(PNPcoord.), JPNP–Ph PCH CH PPh ¼ 17 Hz]; 26.90 [d, (Ph2P-
ꢀ2.577 eA for 5. In the case of 1 one of the CHCl3 mol-
2
2
2
2
3
CH2CH2PPh2), JPNP–Ph PCH CH PPh ¼ 17 Hz]. MS (m/e):
ecules is disordered. The C–H hydrogen atoms for this sol-
vent have not been included. Suitable crystals of 1a were
obtained from CDCl3 at 25 ꢁC for several days; while crys-
tals for 1, 3, and 5 were obtained from a 1:1 mixture of
CHCl3/hexane at ꢀ10 ꢁC. Adequate crystals of 2 were
grown from a CH2Cl2/hexane 1:1 solution at 4 ꢁC. There
are two independent molecules in the asymmetric unit of
complex 2. Adequate crystals of 4 were grown from a
THF solution at 4 ꢁC. There are three THF molecules in
the asymmetric unit of 4, one of them is disordered. The
molecule is located at a crystallographic special position.
2
2
2
2
1211 [M]+; 1155 [Mꢀ(CO)]+; 1127 [Mꢀ2(CO)]+; 669 [Mꢀ
PNP]+; 641 [MꢀPNPꢀ(CO)]+; 585 [MꢀPNPꢀ3(CO)]+.
2.1.3. Method C
A 100 mL round bottom flask was charged with 70 mL
of dry toluene, [ReBr(CO)5] (0.5 g, 1.23 mmol), and PPh3
(0.32 g, 1.23 mmol). After 30 min at reflux temperature
the phosphine substitution complex [ReBr(CO)4{PPh3}]
was the major product detected by IR m(CO). The reaction
was allowed to stand at room temperature (25 ꢁC) for
around 10 min. K[N(SePPh2)2] (0.72 g, 1.23 mmol) was
added and the reaction mixture set to reflux temperature
for 30 min. Toluene was removed under reduced pressure
leaving a whitish powder. KBr was filtered off from a solu-
tion of 25 mL of dichloromethane. Elimination of dichlo-
romethane under reduced pressure and crystallization
from a mixture of hexane/dichloromethane afforded com-
plex 1 in 84% yield (1.11 g, 1.03 mmol).
3. Results and discussion
3.1. Syntheses
Complex 1, [Re(CO)3(PPh3){Ph2P(Se)NP(Se)Ph2-j2Se}],
was prepared by three methods: in Method A [ReBr(CO)5],
PPh3, and K[N(SePPh2)2] were reacted under toluene reflux
for 30 min (see Scheme 1 for the three methods). Method B
consisted in the formation of [Re(CO)4{Ph2P(Se)NP-
(Se)Ph2-j2Se}] [11c] followed by addition of PPh3 to give
1; the reaction time amounted to 1 h and 50 min. Prepara-
tion of [ReBr(CO)4{PPh3}] and subsequent reaction in situ
with K[N(SePPh2)2] constituted Method C with a total
reaction time of 1 h. Reaction times were determined by
IR spectroscopy monitoring in the m(CO) region.
2.2. Crystal data
See Tables 1–3.
2.3. Crystal structure determinations
Data for complexes 1–5 were collected at 100(2) K on a
Bruker Smart Apex CCD diffractometer and used in the
From Scheme 1, it can be seen that the best route for the
preparation of complex 1 is Method A (greatest yield and
Table 1
Crystal data for 1 and 1a
1
1a
Empirical formula
M
C
1373.2
47.5H37.5Cl7.5NO3P3ReSe2
C45H35NO3P3ReSe2
074.77
Temperature (K)
Crystal size (mm)
Crystal system
Space group
100(2)
0.42 · 0.25 · 0.21
Monoclinic
P21/c
100(2)
0.42 · 0.39 · 0.06
Triclinic
ꢀ
P1
˚
a (A)
22.924(3)
9.6096(7)
˚
b (A)
10.354(1)
24.049(3)
9.7098(8)
21.298(2)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
116.42(1)
90
92.120(1)
94.819(1)
93.196(1)
1975.5(3)
3
˚
V (A )
5112.4(10)
Z
4
2
h Range for data collection (ꢁ)
Reflections collected
1.70–25.00
25784
1.92–25.00
19060
Independent reflections (Rint
Final R indices [F2 > 2r(F2)]
R indices (all data)
)
8794 (0.0419)
R1 = 0.0407, wR2 = 0.0984
R1 = 0.0463, wR2 = 0.1012
6945 (0.0535)
R1 = 0.0366, wR2 = 0.0850
R1 = 0.0401, wR2 = 0.0872

1702
L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
Table 2
Crystal data for 2 and 3
2
3
Empirical formula
M
C40H33NO3P3ReSe2
1012.7
C35H31NO3P3ReSe2 Æ CHCl3
1070.1
Temperature (K)
Crystal size (mm)
Crystal system
Space group
100(2)
100(2)
0.37 · 0.31 · 0.26
Monoclinic
P21/c
0.42 · 0.36 · 0.24
Monoclinic
P21/c
˚
a (A)
22.815(2)
10.500(1)
˚
b (A)
17.082(1)
17.058(2)
˚
c (A)
24.623(2)
22.056(3)
b (ꢁ)
110.763(1)
7515.3(11)
102.676(2)
3854.1(8)
3
˚
V (A )
Z
8
4
h Range for data collection (ꢁ)
Reflections collected
1.53–26.00
77313
1.52–25.00
36043
Independent reflections (Rint
Final R indices [F2 > 2r(F2)]
R indices (all data)
)
14748 (0.0823)
R1 = 0.0524, wR2 = 0.1030
R1 = 0.0676, wR2 = 0.1094
6798 (0.0548)
R1 = 0.0315, wR2 = 0.0767
R1 = 0.0332, wR2 = 0.0780
Table 3
Crystal data for 4 and 5
4
5
Empirical formula
M
C
80H64N2O6P6Re2Se4 Æ 6THF
C53H44NO3P4ReSe2 Æ CHCl3
1330.26
2456.02
Temperature (K)
Crystal size (mm)
Crystal system
Space group
100(2)
100(2)
0.36 · 0.42 · 0.48
Triclinic
0.24 · 0.22 · 0.18
Monoclinic
P21/c
11.0339(7)
26.733(2)
17.183(1)
ꢀ
P1
˚
a (A)
11.1159(7)
13.1897(8)
18.363(1)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
87.265(1)
87.644(1)
86.650(1)
3854.1(8)
94.045(1)
3
˚
V (A )
5055.7(5)
Z
2
2
h Range for data collection (ꢁ)
Reflections collected
1.41–25.00
24359
1.55–25.00
25692
Independent reflections (Rint
Final R indices [F2 > 2r(F2)]
R indices (all data)
)
8842 (0.0541)
R1 = 0.0506, wR2 = 0.0957
R1 = 0.0654, wR2 = 0.1011
9404 (0.0392)
R1 = 0.0477, wR2 = 0.1322
R1 = 0.0505, wR2 = 0.1343
shortest reaction time). Similar results were obtained with
PMePh2 and PMe2Ph. The complexes here reported are
stable in the solid state and no decomposition was observed
after several days in solution.
In an attempt to prepare the spiro complex [Re(CO)2-
(Ph2PCH2CH2PPh2-j2P){Ph2P(Se) NP(Se)Ph2-j2Se}] we
carried out the reaction shown in Eq. (1) in equimolar
amounts
Method A: i
PPh3
OC
OC
Se
Se
Method B: ii
[ReBr(CO)5]
Re
iii
CO
Method C: iv
v
Se Se = Ph2P(Se)NP(Se)Ph2
Scheme 1. All reactions’ steps were conducted under toluene reflux. (i) K[N(SePPh2)2], PPh3, 30 min, 98% yield. (ii) K[N(SePPh2)2], 20 min. (iii) PPh3, 1 h,
90% yield. (iv) PPh3, 30 min. (v) K[N(SePPh2)2, 30 min, 84% yield.

L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
1703
The m(PSe) vibration in (H[N(SePPh2)2]) appears at 595
and 546 cmꢀ1 in KBr [2]; in complexes 1–5 the correspond-
ing band appears between 536 and 539 cmꢀ1. Complex 5
shows at 553 cmꢀ1 a band arising from the non coordi-
nated P@Se moiety.
½ReBrðCOÞ5ꢁ þ Ph2PCH2CH2PPh2 þ K½NðSePPh2Þ2ꢁ ð1Þ
After 5 h of reaction a mixture of complexes 4 and 5 was
detected being 5 the major product. Complex 4 could be
prepared with 70% yield starting from [Re(CO)4{Ph2P-
(Se)NP(Se)Ph2-j2Se}] and an equimolar amount of
Ph2PCH2CH2PPh2 under toluene reflux for 5 h (Method
B). Complex [Re(CO)3(Ph2PCH2CH2PPh2-j2P){Ph2P(Se)-
NP(Se)Ph2-jSe}], 5, was obtained in 50% yield when half
the equimolar amount of Ph2PCH2CH2PPh2 was added
to a toluene solution of [Re(CO)4{Ph2P(Se)NP(Se)Ph2-
j2Se}] and set to reflux for 30 min. These results contrast
with the reactivity of [Mn(CO)4{Ph2P(Se)NP(Se)Ph2-
j2Se}] with Ph2PCH2CH2PPh2, where the complex
spiro-[Mn(CO)2(Ph2PCH2CH2PPh2-j2P){Ph2P(Se)NP(Se)
Ph2-j2Se}] was isolated with 74% using equimolar amounts
of the starting materials [11a]. The impossibility of elimina-
tion of one CO group by the Se atom in 5 precludes the
formation of spiro-[Re(CO)2 (Ph2PCH2CH2PPh2-j2P)-
{Ph2P(Se)NP(Se) Ph2-j2Se}]. So far no manganese analogs
of 4 or 5 are known; although the manganese analog of 4
has been proposed as an intermediate to spiro-[Mn(CO)2-
(Ph2PCH2CH2PPh2-j2P){Ph2P(Se)NP(Se)Ph2-j2Se}] [11a].
3.3. NMR spectroscopy
Complexes 1–3 show symmetrical coordination of the
Ph2P(Se)NP(Se)Ph2 ligand in solution as evidenced by the
appearance of one signal in 31P and 77Se NMR spectra.
The 77Se NMR chemical shifts do not show any trend; it
is expected that accumulation of more 77Se NMR data will
unfold the governing effects on the chemical shifts in these
systems. Notwithstanding, we note that 77Se NMR not
only reflects the symmetry in complexes 1–3, but also gave
insight into the interaction of the P–Se atoms through the
1JP–Se coupling constants (Table 4).
The P–Se coupling constant values vary in the order
[Re(CO)4{Ph2P(Se)NP(Se)Ph2-j2Se}] < 1 ꢂ 2 ꢂ 3 < HN-
(SePPh2)2. The higher electron density at the metal center
in complexes 1, 2, and 3 compared with [Re(CO)4{Ph2P-
(Se)NP(Se)Ph2-j2Se}] leads to a stronger interaction of
the P–Se atoms in the Ph2P(Se)NP(Se)Ph2 ligand as evi-
3.2. Infrared spectroscopy
1
denced by the JP–Se coupling constants. The strongest P–
Se interaction is observed in the acid HN(SePPh2)2, where
the selenium and phosphorus atoms are bound displaying a
Complexes 1–3 and 5 present three bands (in solution) in
the m(CO) carbonyl region corresponding to the 2A0 + A00
vibration modes [24] arising from the carbonyl groups’
local symmetry with a Cs point group. The carbonyl group
IR pattern is assigned to mononuclear complexes with fac
disposition. In the case of 1–3 both selenium atoms of the
PNP ligand bind to the metal center; while in 5 the PNP
ligand is attached to the rhenium by only one selenium
atom. The IR spectrum of 4 shows three carbonyl bands
(2020s, 1936s, and 1904m cmꢀ1 in CHCl3) arising from a
fac arrangement at each metal center of the dinuclear com-
plex. A comparison of the IR carbonyl band frequencies
between 4 and 5 (2035s, 1964s, and 1918m cmꢀ1 in CHCl3)
shows a greater electron density at the metal center of 4.
This can be accounted for by a stronger p acidity of
Ph2PCH2CH2PPh2 with respect to the PNP ligand and/or
a stronger r donor capacity of the latter.
1
1JP–Se of 788 Hz. Interestingly, the JP–Se coupling con-
stants do not seem to be sensitive to the oxidation state
of the metal to which the N(SePPh2)2 ligand is attached
as shown in Table 4; where a set of Re(V) complexes exhi-
1
bit similar JP–Se coupling constants to those reported in
this work.
3.4. Structural studies
The geometry around the rhenium center in the com-
plexes herein reported is slightly distorted octahedral with
the carbonyl groups in fac disposition. The molecular
structure of 1 including its atom numbering scheme is
shown in Fig. 1 together with some selected bond distances
and angles.
Table 4
77Se NMR shifts and coupling constants in CDCl3
Compound
d (ppm)
1JP–Se/Hz
Reference
[Re(CO)4{Ph2P(Se)NP(Se)Ph2j2Se}]
1
ꢀ340.1
546
559
560
561
525
532, 540
558
547
788
[11c]
ꢀ276.5
This work
This work
This work
[11e]
[11d]
[11d]
2
ꢀ289.4
3
ꢀ298.3
[ReO(Cl){Ph2P(Se)NP(Se)Ph2j2Se}2]a
cis-Re(NMe)Cl2{Ph2P(Se)NP(Se)Ph2j2Se}-(PPh3)]
[Re(NMe)Cl{Ph2P(Se)NP(Se)Ph2j2Se}2]
[ReN{Ph2P(Se)NP(Se)Ph2j2Se}2]
HN(SePPh2)2
–
–
–
–
[11d]
ꢀ156.6
a
In CD2Cl2.

1704
L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
C18
C19
C19
C9
C18
C7
C6
C5
C17
C20
C8
C7
C8
C9
C20
C17
O1
C6
C4
O1
C16
C21
P2
C4
C5
P1
N1
C21
C27
C16
C11
C22
C1
C11
C26
C1
C12
P1
C12
C13
C10
C13
C10
N1
C22
C15
Se1
P2
C25
O2
C2
O3
C15
C14
Re1
C3
C27
C2
Se1
O2
C14
C24
Re1
O3
C24
C23
Se2
C26
C3
C23
Se2
C25
C39
C34
P3
C38
C39
C41
C45
P3
C41
C42
C37
C38
C29
C40
C34
C40
C33
C32
C35
C43
C28
C36
C42
C35
C28
C37
C44
C30
C36
C29
C33
C31
C43
C31
C44
C45
C30
C32
Fig. 1. Molecular structure of 1 including atom numbering scheme
(ORTEP drawing with 50% probability ellipsoids). Selected bond lengths
Fig. 2. Molecular structure of 1a including atom numbering scheme
(ORTEP drawing with 50% probability ellipsoids). Selected bond lengths
˚
(A) and angles (ꢁ): Re(1)–Se(1) 2.6382(6), Re(1)–Se(2) 2.6277(6), Se(1)–
˚
(A) and angles (ꢁ): Re(1)–Se(1) 2.6403(5), Re(1)–Se(2) 2.6318(5), Se(1)–
P(1) 2.193(2), P(1)–N(1) 1.594(5); P(1)–N(1)–P(2) 128.7(3), Se(1)–Re(1)–
Se(2) 91.18(2), N(1)–P(1)–Se(1) 117.8(2), P(1)–Se(1)–Re(1) 105.82(4).
P(1) 2.174(1), P(1)–N(1) 1.590(4); P(1)–N(1)–P(2) 133.6(3), Se(1)–Re(1)–
Se(2) 95.15(2), N(1)–P(1)–S e(1) 119.8(2), P(1)–Se(1)–Re(1) 106.06(4).
C7
C8
When complex 1 was left in CDCl3 at 25 ꢁC for several
days, in an nmr tube, suitable crystals for the X-ray struc-
tural analysis of 1a were obtained. The molecular structure
of 1a including its atom numbering scheme is shown in
Fig. 2 together with some selected bond distances and angles.
The six-membered metallacycle SePNPSeRe in com-
plexes 1 and 1a differ in conformation: in 1 the ring pre-
sents a chair conformation, while in 1a the boat
conformation is observed. The nitrogen and the rhenium
atoms are positioned at the apices in both rings. The
change in conformation can be ascribed to the higher tem-
perature at which crystals were grown.
The molecular structures of 2 and 3 including their atom
numbering scheme are shown in Figs. 3 and 4, respectively,
together with some selected bond distances and angles.
In the asymmetric unit of 2 there are two independent
molecules whose structures are similar. The SePNPSeRe
ring conformation in 2 can be best described as a half chair
and in 3 the conformation is that of a chair. The chair con-
formation is shared by the dinuclear complex 4 (the molec-
ular structure of 4 including its atom numbering scheme is
shown in Fig. 5 together with some selected bond distances
and angles).
C12
C9
C6
C11
C4
C37
C36
C13
C5
O2
C38
C10
Se1
C14
P1
O1
C2
C39
P3
C35
C15
N1
C34
Re1
C1
C21
C26
C25
C40
O3
C3
C27
C33
C28
C16
P2
C20
Se2
C22
C24
C23
C32
C29
C19
C17
C30
C31
C18
Fig. 3. Molecular structure of 2 including atom numbering scheme
(ORTEP drawing with 50% probability ellipsoids). Selected bond lengths
(A) and angles (ꢁ): Re(1)–Se(1) 2.6386(7), Re(1)–Se(2) 2.6451(7), Se(1)–
P(1) 2.171(2), P(1)–N(1) 1.594(6); P(1)–N(1)–P(2) 138.4(4), Se(1)–Re(1)–
˚
Se(2) 88.43(2), N(1)–P(1)–Se(1) 119.1(2), P(1)–Se(1)–Re(1) 99.98(5).
˚
2.175(1) and 1.592(5) A in complexes 1, 1a–4). In
The diselenoimidodiphosphinato ligand is symmetrically
coordinated to Re through both selenium atoms in com-
plexes 1, 1a–4; the Re–Se bond lengths are equivalent
Ph2P(Se)NHP(Se)Ph2 neither the P–Se nor the P–N bond
˚
lengths are symmetrical (P–Se = 2.085(1), 2.101(1) A and
˚
P–N = 1.678(4), 1.686(3) A [17]); the lengthening of both
˚
within experimental error (av. 2.6396(6) A for complexes
–P–Se bond distances as well as the shortening of both
P–N bond distances in complexes 1, 1a–4 are indicative
of electron delocalization over the ReSe2P2N metallacycle.
The difference in the PNP angles attests to the flexibility of
1, 1a–4) indicating a covalent interaction (Rcov (Re, Se) =
˚
2.76 A) [25]. The P–Se and P–N bond distances in the SeP-
NPSe backbone are also equivalent (av. P–Se and P–N:

L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
1705
O3
C6
C7
C8
C18
C30
P4
C3
C19
C5
C4
C48
C17
C9
C1
C20
O1
N1
Re1
P3
O1
C15
C13
C29
C12
C10
C11
C21
C14
O2
P1
C16
C4
C2
C1
N1
C36
C28
C27
C22
Se1
P2
C2
O2
Re1
C26
P1
Se2
C23
C42
Se1
P2
C16
C25
C24
C3
O3
Se2
C10
P3
C34
C35
C22
C28
Fig. 6. Molecular structure of 5 with atom numbering scheme (ORTEP
drawing with 50% probability ellipsoids). Selected bond lengths (A) and
C33
˚
C29
angles (ꢁ); Re(1)–Se(2) 2.6227(7), Se(1)–P(1) 2.106(2), Se(2)–P(2) 2.180(2),
P(2)–N(1) 1.579(6), N(1)–P(1) 1.601(6); P(1)–N–P(2) 130.2(4). Only ipso
carbons are shown for clarity.
C32
C30
C31
Fig. 6 shows a three dimensional representation with
corresponding atom numbering scheme and some selected
bond lengths and angles of complex 5.
Fig. 4. Molecular structure of 3 including atom numbering scheme
(ORTEP drawing with 50% probability ellipsoids). Selected bond lengths
˚
(A) and (ꢁ): Re(1)–Se(1) 2.6485(5), Re(1)–Se(2) 2.6450(5), Se(1)–P(1)
2.180(1), P(1)–N(1) 1.598(4); P(1)–N(1)–P(2) 134.7(2), Se(1)–Re(1)–Se(2)
88.80(2), N(1)–P(1)–Se(1) 119.7(1), P(1)–Se(1)–Re(1) 102.45(3).
The inorganic selenium ligand in 5 binds in a monoden-
tate fashion. The P–Se bond distance is shorter for the
uncoordinated P–Se than for the coordinated P–Se group
˚
(2.106(2) vs. 2.180(2) A, resp.). Bis(diphenylphosphine)eth-
the SePNPSe backbone (PNP angle of 1 = 128.7(3)ꢁ and
PNP angle of 2 = 138.4(4)ꢁ; lowest and greatest PNP angle,
respectively): from existing data no trend between PNP
angle and ring conformation can be drawn.
ane coordinates to build a five-membered ring. The PNP
angle in complex 5 measures 130.2(4)ꢁ; and is greater than
the corresponding PNP angle in 1; although in the latter
O3A
O2A
C3A
C2A
C34A
O1A
C22
C1A
C28A
C10
Re1A
P3A
C4A
N1
P2
Se1A
Se2A
C40
C16
Se1
P1
O1
C16A
Se2
C40A
P1A
C4
N1A
P2A
Re1
C3
C1
C10A
P3
C28
C22A
C34
O3
C2
O2
˚
Fig. 5. Molecular structure of 4 including atom numbering scheme (ORTEP drawing with 50% probability ellipsoids). Selected bond lengths (A) and
angles (ꢁ): Re(1)–Se(1) 2.6450(7), Re(1)–Se(2) 2.6356(7), Se(1)–P(1) 2.160(2), P(1)–N(1) 1.594(5); P(1)–N(1)–P(2) 135.7(4), Se(1)–Re(1)–Se(2) 88.09(2),
N(1)–P(1)–Se(1) 118.0(2), P(1)–Se(1)–Re(1) 101.12(5). Only ipso carbons are shown for clarity.

1706
L. Ma´rquez-Pallares et al. / Journal of Organometallic Chemistry 692 (2007) 1698–1707
[5] (a) K. Darwin, L.M. Gilby, P.R. Hodge, B. Piggott, Polyhedron 18
(1999) 3729–3733;
the inorganic ligand N(SePPh2)2 chelates to form a
matallacycle.
´
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j2Se}] was found. Although an understanding of the effects
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CCDC 629243, 629244, 629245, 629246, 629247 and
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for 1, 1a, 2, 3, 4 and 5. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
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´
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The authors thank Messrs E. Garcıa-Rıos, L. Velasco-
Ibarra, and M.N. Zavala-Segovia for technical assistance
(Instituto de Quımica, UNAM) and Dr. Vojtech Jancik
´
for invaluable help with some X-ray crystal structure deter-
minations. N.Z.-V. gratefully acknowledges funding from
PAPIIT (DGAPA-UNAM) through grant IN217706-2
and the CONACyT through Grant P47263-Q. M.G.-R.
thanks UNAM for a postdoctoral stipend. M.R.-L. deeply
acknowledges a Ph.D. stipend from CONACyT through
Grant P47263-Q. L.M.-P. thanks PAPIIT (DGAPA-
UNAM) for an undergraduate stipend through Grant
IN217706-2.
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