Bis(diphenylphosphino)amine and their dichalcogenide derivatives as ligands in rhodium(III), iridium(III), and ruthenium(II) complexes. Crystal structures of [(η5-C5Me5)MCl{η 2-(SePPh2)2N}]

Article abstract of DOI:10.1016/S0022-328X(00)00088-7

Reaction of the dimers [{(η⁵-C₅Me₅)MCl}₂(μ-Cl) ₂] (M = Rh, Ir) or [{(η⁶-arene)RuCl}₂(μ-Cl)₂] (arene = p-MeC₆Hⁱ₄Pr, C₆Me

Full text of DOI:10.1016/S0022-328X(00)00088-7

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 607 (2000) 3–11
Bis(diphenylphosphino)amine and their dichalcogenide derivatives
as ligands in rhodium(III), iridium(III), and ruthenium(II)
complexes. Crystal structures of [(h5-C5Me5)MCl{h2-(SePPh2)2N}]
(M=Rh, Ir)
Mauricio Valderrama a, Rau´l Contreras a, M. Pilar Lamata b, Fernando Viguri b,
Daniel Carmona c, Fernando J. Lahoz c, Sergio Elipe c, Luis A. Oro c,*
a Departamento de Qu´ımica Inorga´nica, Facultad de Qu´ımica, Pontificia Uni6ersidad Cato´lica de Chile, Casilla 306, Santiago-22, Chile
b Departamento de Qu´ımica Inorga´nica, Escuela Uni6ersitaria de Ingenier´ıa Te´cnica e Industrial, Instituto de Ciencia de Materiales de Arago´n,
Uni6ersidad de Zaragoza-CSIC, Corona de Arago´n 35, 50009 Zaragoza, Spain
c Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received 29 December 1999; received in revised form 25 January 2000
This article is dedicated to Professor Martin A. Bennett, author of major advances on Organometallic Chemistry, on the occasion of his 65th
birthday.
Abstract
Reaction of the dimers [{(h5-C5Me5)MCl}2(m-Cl)2] (M=Rh, Ir) or [{(h6-arene)RuCl}2(m-Cl)2] (arene=p-MeC6Hi4Pr, C6Me6)
with NH(PPh2)2 in the presence of AgA (A=BF4, PF6) leads to the mononuclear cationic complexes [(h5-C5Me5)MCl{h2-
(PPh2)2NH}]A (M=Rh (1), Ir (2)) or [(h6-arene)RuCl{h2-(PPh2)2NH}]A (arene=p-MeC6Hi4Pr (3), C6Me6 (4)). Similar reactions
using the chalcogenide derivatives NH(EPPh2)2 (E=S, Se) yield the neutral complexes [(h5-C5Me5)RhCl{h2-(EPPh2)2N}] (E=S
(5), Se (6)), [(h5-C5Me5)IrCl{h2-(EPPh2)2N}] (E=S (7), Se (8)), [(h6-arene)RuCl{h2-(SPPh2)2N}] (arene=C6H6 (9), p-MeC6Hi4Pr
(10)) and [(h6-arene)RuCl{h2-(SePPh2)2N}] (arene=C6Me6 (11), p-MeC6Hi4Pr (12)). Chloride abstraction from complexes 5–8
with AgPF6 in the presence of PPh3 gives the cationic complexes [(h5-C5Me5)Rh{h2-(EPPh2)2N}(PPh3)]PF6 (E=S (13), Se (14))
and [(h5-C5Me5)Ir{h2-(EPPh2)2N}(PPh3)]PF6 (E=S (15), Se (16)). Complexes 13–16 can also be synthesised from the starting
dinuclear complexes, AgPF6, NH(EPPh2)2 and PPh3. Using this alternative synthetic route the related ruthenium complexes
[(h6-C6Me6)Ru{h2-(EPPh2)2N}(C5H5N)] BF4 (E=S (17), Se (18)) can be prepared. All described compounds have been
characterised by microanalysis and NMR (1H, 31P) and IR spectroscopy. The crystal structures of the neutral complexes
[(h5-C5Me5)MCl{h2-(SePPh2)2N}] (M=Rh (6), Ir (8)) have been determined by X-ray diffraction methods. Both complexes
exhibit analogous pseudo-octahedral molecular structures with a C5Me5 group occupying three coordination positions and a
bidentate chelate Se,Se%-bonded ligand and a chloride atom completing the coordination sphere. © 2000 Elsevier Science S.A. All
rights reserved.
Keywords: Rhodium; Iridium; Ruthenium; Bis(diphenylphosphino)amine complexes; Dichalcogenide complexes; Crystal structures
1. Introduction
erties. In a similar fashion to the widely employed
bis(diphenylphosphino)methane, the dppa ligand can
bind to metal atoms in different ways: monodentate [1],
chelating [2], single bridging [3], double bridging [1,4] or
tridentate bridging in its anionic form [5].
On the other hand, its chalcogenide derivatives can
be regarded as non-carbon analogues of acetylacetones
and their deprotonation reactions give the anions
[(EPPh2)2N]− which undergo complexation with many
The chemistry of the bis(diphenylphosphino)amine
(NH(PPh2)2, dppa) and its chalcogenide derivatives
(NH(EPPh2)2; E=O, S, Se) has been rapidly developed
in recent years due to their versatile coordination prop-
* Corresponding author. Tel./fax: 34-976-761143.
E-mail address: oro@posta.unizar.es (L.A. Oro).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00088-7

4
M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
metals to form inorganic (carbon-free) chelate rings [6].
A variety of transition metal compounds have been
characterised crystallographically, showing that the lig-
ands form non-planar metallacycles, in some cases with
unusual coordination geometries at the metal centre [3].
The majority of the coordination studies have been
developed with the sulphur derivative [(SPR2)2N]− due
to the flexibility of the SꢀPꢀNꢀPꢀS backbone and its
2.1. Preparation of complexes
2.1.1. [(p5-C5Me5)MCl{p2-(PPh2)2NH}]PF6 (M=Rh
(1a), Ir (2a))
To a solution of the dinuclear complex [{(h5-
C5Me5)MCl}2(m-Cl)2] (0.162 mmol; Rh (100 mg), Ir
(126 mg)) in CH2Cl2 (10 cm3) was added a solution of
AgPF6 (82 mg; 0.324 mmol) in Me2CO (10 cm3). After
stirring the mixture for 1 h at room temperature (r.t.),
in the absence of light, the precipitated silver chloride
was removed by filtration through Kieselghur. To the
filtrate, NH(PPh2)2 (125 mg; 0.324 mmol) was added
and the mixture stirred for 2 h. The resulting solution
was evaporated to a small volume and the complex
precipitated by adding n-hexane or pentane. The red
solids were filtered off, washed with n-hexane and
diethyl ether and dried under vacuum. Complex 1a:
yield, 208 mg, 84% (Found: C, 50.8; H, 5.1; N, 1.7.
C34H36ClF6NP3Rh requires C, 50.8; H, 4.5; N, 1.7%).
wmax/cm−1 (KBr) 3423 (NH), 838, 558 (PF6−). lH
,
large S···S bite (3.7–4.0 A). This bite is larger than that
of 1,1-dithio ligands, R2PS−2 (ca. 3.0 A), which presents
,
some uses in metal extractions, oil additives or biologi-
cal activities [4]. However, only a few examples of
transition metal dichalcogenoimidophosphinate com-
plexes containing organometallic moieties have been
described so far, [AuR2{(SPPh2)2N}] [5], [Mn(CO)4-
{(SPPh2)2N}] [4a] or [Rh(cod){(SePPh2)2N}] [4b] being
some representative examples.
Here we describe the synthesis of cationic complexes
of the type [(hn-ring)MCl(h2-P,P%-dppa)]A [(hn-ring)-
M=(h5-C5Me5)Rh, (h5-C5Me5)Ir, (h6-p-MeC6Hi4Pr)-
Ru, (h6-C6Me6)Ru; A=PF6, BF4], neutral complexes
of the type [(hn-ring)MCl{h2-(EPPh2)2N}] [(hn-
ring)M=(h5-C5Me5)Rh, (h5-C5Me5)Ir, (h6-C6H6)Ru,
(h6-p-MeC6H4i Pr)Ru, (h6-C6Me6)Ru; E=S, Se] [7] and
cationic complexes of general formula [(h5-C5Me5)-
M{h2-(EPPh2)2N}(PPh3)]PF6 (M=Rh, Ir; E=S, Se)
and [(h6-C6Me6)Ru{h2-(EPPh2)2N}(C5H5N)]BF4 (E=
S, Se). The crystal structure of complexes [(h5-
C5Me5)MCl{h2-(SePPh2)2N}] (M=Rh, Ir), determined
by single-crystal X-ray diffraction, are also reported.
4
(CDCl3) 1.49 [t, 30 H, C5Me5, J(PH)=4.1 Hz], 7.24–
7.59 (m, 20 H, Ph). lP (CDCl3) 48.5 [d, 1J(RhP)=118.5
1
Hz], −145.0 [sp, PF−6 , J(PF)=714 Hz]. Complex 2a:
yield, 176 mg, 61% (Found: C, 45.7; H, 4.1; N, 1.7.
C34H36ClF6IrNP3 requires C, 45.7; H, 4.1; N, 1.6%).
wmax/cm−1 (KBr) 3443 (NH), 839, 560 (PF6−). lH
4
(CDCl3) 1.54 [t, 30 H, C5Me5, J(PH)=2.7 Hz], 6.86–
7.73 (m, 20 H, Ph), 8.8 (s, br, 1 H, NH). lP (CDCl3)
1
16.8 (s), −145.0 [sp, PF−6 , J(PF)=714 Hz].
The related tetrafluoroborate complexes [(h5-
C5Me5)RhCl{h2-(PPh2)2NH}]BF4 (1b) and [(h5-
C5Me5)IrCl{h2-(PPh2)2NH}]BF4 (2b), were prepared
using AgBF4 (63 mg; 0.324 mmol) instead of AgPF6, in
CHCl3/Me2CO: 5/15 cm3. The products were recrys-
tallised from dichloromethane–diethyl ether. Complex
1b: yield, 159 mg, 62% (Found: C, 52.6; H, 3.7; N, 2.0.
C34H36BClF4NP2Rh·0.5CH2Cl2 requires C, 52.6; H, 4.0;
N, 1.8%). wmax/cm−1 (KBr) 3424 (NH), 1103 and 516
2. Experimental
All reactions were carried out under purified nitrogen
by using Schlenk-tube techniques. Solvents were dried,
distilled, and stored under a nitrogen atmosphere. The
starting materials [{(h5-C5Me5)MCl}2(m-Cl)2] (M=Rh,
Ir) [8], [{(h6-arene)RuCl}2(m-Cl)2] (arene=C6H6 [9], p-
MeC6Hi4Pr [10], C6Me6 [10]), and the ligands
NH(PPh2)2 and NH(EPPh2)2 [4b,11] were prepared by
published procedures. Elemental analyses (C, H, N, and
S) were made with a Perkin–Elmer 240C microanaly-
ser. IR spectra were recorded on a Perkin–Elmer 1330
spectrophotometer using Nujol mulls between
polyethylene sheets. The NMR spectra were recorded
on Bruker AC-200P and Varian Unity 300 spectrome-
ters. Chemical shifts are reported in ppm relative to
SiMe4 (1H) and 85% H3PO4 in D2O (31P, positive shifts
downfield) as internal and external standards, respec-
tively. Mass spectra were measured on a VG Autospec
double-focusing mass spectrometer operating in the
FAB+ mode; ions were produced with the standard
Cs+ gun at ca. 30 kV and 3-nitrobenzylalcohol (NBA)
was used as matrix.
4
(BF−4 ). lH (CD2Cl2) 1.53 [t, 30 H, C5Me5, J(PH)=4.1
Hz], 7.30–7.63 (m, 20 H, Ph). lP (CD2Cl2) 49.8 [d,
1J(RhP)=118.4 Hz]. Complex 2b: yield, 217 mg, 81%
(Found: C, 48.2; H, 3.9; N, 1.7. C34H36BClF4IrNP2
requires C, 48.9; H, 4.4; N, 1.7%). wmax/cm−1 (KBr)
3442 (NH), 1105 and 519 (BF−4 ). lH (CDCl3) 1.54 [t, 30
4
H, C5Me5, J(PH)=2.7 Hz], 6.86–7.73 (m, 20 H, Ph)
and 8.7 (s, br, 1 H, NH). lP (CDCl3) 16.7 (s).
2.1.2. [(p6-p-MeC6H4i Pr)RuCl{p2-(PPh2)2NH}]BF4 (3)
To a solution of the binuclear ruthenium complex
[{(h6-p-MeC6H4i Pr)RuCl}2(m-Cl)2] (100 mg; 0.163
mmol) in CHCl3 (5 cm3) was added a solution of
AgBF4 (64 mg; 0.326 mmol) in Me2CO (15 cm3). After
stirring the mixture for 1 h at r.t., in the absence of
light, the precipitated silver chloride was removed by
filtration through Kieselghur. To the filtrate,
NH(PPh2)2 (126 mg; 0.326 mmol) was added and the

M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
5
mixture stirred for 2 h. The resulting solution was
evaporated to a small volume and the complex precipi-
tated by adding n-hexane or pentane. The solid was
filtered off, washed with n-hexane and diethyl ether and
dried under vacuum. Yield: 220 mg, 86% (Found: C,
52.5; H, 4.6; N, 1.9. C34H35BClF4NP2Ru·0.5CH2Cl2
requires C, 52.7; H, 4.6; N, 1.8%). wmax/cm−1 (KBr)
3442 (NH), 1102 and 519 (BF−4 ). lH (CDCl3) 0.89 [d, 6
(m, 20 H, Ph). lP (CDCl3) 31.6 (s). Complex 8: yield,
124 mg, 65% (Found: C, 45.3; H, 4.0; N, 1.5.
C34H35ClIrNP2Se2 requires C, 45.1; H, 3.9; N, 1.6%).
wmax/cm−1 (Nujol) 530 (PSe), 1170 and 780 (P2N). lH
(CD2Cl2) 1.37 (s, 30 H, C5Me5), 7.05–8.20 (m, 20 H,
1
Ph). lP (CD2Cl2) 18.4 (s, J(PSe)=578 Hz).
2.1.5. [(p6-arene)RuCl{p2-(EPPh2)2N}] (E=S;
H, Me(iPr), J(HH)=6.5 Hz], 1.78 [s, 3 H, Me], 2.13
arene=C6H6 (9), p-MeC6Hi4Pr (10). E=Se;
3
[sp, 1 H, CH(iPr)], 5.20 and 5.30 [4 H, AB system,
J(HH)=5.8 Hz], 5.41 [t, NH, 2J(PH)=4.65 Hz], 7.16–
7.75 (m, 20 H, Ph). lP (CDCl3) 60.7 (s).
arene=C6Me6 (11), p-MeC6Hi4Pr (12))
To a solution of the binuclear complex [{(h6-
arene)RuCl}2(m-Cl)2] (0.1 mmol; C6H6 (49 mg), p-
MeC6Hi4 Pr (61 mg), C6Me6 (67 mg)) in CH2Cl2 (10
cm3) a solution of AgBF4 (41 mg; 0.21 mmol) in
Me2CO (10 cm3) was added. After stirring the mixture
for 1 h, the AgCl formed was filtered off through
Kieselguhr. The filtrate was treated with the ligand
NH(EPPh2)2 (0.2 mmol; E=S (90 mg), Se (108 mg))
and the resulting solution stirred for 2 h. During this
time the solution changed from red to a sort of green
colour. The solution was evaporated to dryness, the
residue extracted with the minimal amount of CH2Cl2
and the solution chromatographed on neutral Al2O3
(90% activity) using CH2Cl2 as eluent. The red solution
obtained was concentrated to a small volume and the
complexes crystallised by careful addition of diethyl
ether. Complex 9: yield, 87 mg, 63% (Found: C, 53.4;
H, 5.2; N, 2.0; S, 9.2. C30H36ClNP2RuS2 requires C,
53.5; H, 5.4; N, 2.1; S, 9.5%). wmax/cm−1 (Nujol) 550
(PS), 1170 and 795 (P2N). lH (CDCl3) 5.17 (s, 6 H,
C6H6), 7.10–8.30 (m, 20 H, Ph). lP (CDCl3) 38.2 (s).
Complex 10: yield, 76 mg, 75% (Found: C, 56.9; H, 4.4;
N 1.9; S, 8.4. C34H34ClNP2RuS2 requires C, 56.8; H,
4.8; N, 2.0; S, 8.9%). wmax/cm−1 (Nujol) 555 (PS), 1180
and 800 (P2N). lH (CDCl3) 1.19 [d, 6 H, Me(iPr),
3J(HH)=6.9 Hz], 2.06 (s, 3 H, Me), 2.78 [m, 1 H,
CH(iPr)], 4.82 and 5.00 [4 H, AB system, J(HH)=5.9
Hz], 7.30–7.88 (m, 20 H, Ph). lP (CDCl3) 36.2 (s).
Complex 11: yield, 78 mg, 62% (Found: C, 51.8; H, 4.7;
N, 1.6. C36H38ClNP2RuSe2 requires C, 51.4; H, 4.6; N,
1.7%). wmax/cm−1 (Nujol) 535 (PSe), 1150 and 780
(P2N). lH (CDCl3) 1.80 (s, 18 H, C6Me6), 6.94–8.10 (m,
20 H, Ph). lP (CDCl3) 24.8 [s, 1J(PSe)=587 Hz].
Complex 12: yield, 212 mg, 80% (Found: C, 50.2; H,
3.9; N, 2.2. C34H34ClNP2RuSe2 requires C, 50.2; H, 4.2;
N, 1.7%). wmax/cm−1 (Nujol) 530 (PSe), 1170 and 780
2.1.3. [(p6-C6Me6)RuCl{p2-(PPh2)2NH}]PF6 (4)
To a solution of complex [{(h6-C6Me6)RuCl}2(m-Cl)2]
(100 mg; 0.15 mmol) in CH2Cl2 (10 cm3) was added a
solution of AgPF6 (76 mg; 0.30 mmol) in Me2CO (10
cm3). The mixture was worked up as described for
complex 3, using 116 mg (0.30 mmol) of the ligand
NH(PPh2)2. Yield: 191 mg, 77% (Found: C, 51.9; H,
4.8; N, 1.7. C36H39ClF6NP3Ru requires C, 52.2; H, 4.8;
N, 1.7%). wmax/cm−1 (KBr) 3443 (NH), 837 and 557
(PF−6 ). lH [(CD3)2CO] 2.07 (s, 18 H, C6Me6), 7.52–7.87
(m, 20 H, Ph). lP [(CD3)2CO] 58.4 (s), −145.0 [sp,
1
PF−6 , J(PF)=714 Hz].
2.1.4. [(p5-C5Me5)MCl{p2-(EPPh2)2N}] (M=Rh;
E=S (5), Se (6). M=Ir; E=S (7), Se (8))
To a solution of the binuclear complex [{(h5-
C5Me5)MCl}2(m-Cl)2] (0.1 mmol; Rh (62 mg), Ir (80
mg)) in CH2Cl2 (10 cm3) a solution of AgBF4 (41 mg;
0.21 mmol) in Me2CO (10 cm3) was added. After
stirring the mixture for 1 h, the AgCl formed was
filtered off through Kieselguhr. The filtrate was treated
with the ligand NH(EPPh2)2 (0.2 mmol; E=S (90 mg),
Se (108 mg)) and the resulting solution stirred for 2 h.
The mixture was evaporated to dryness and the residue
extracted with the minimal amount of CH2Cl2. The
solution was chromatographed on neutral Al2O3 (90%
activity) using CH2Cl2 as eluent. The red solution ob-
tained was concentrated to a small volume and the
complexes crystallised by careful addition of diethyl
ether. Complex 5: yield, 176 mg, 75% (Found: C, 56.3;
H, 4.8; N, 2.0; S, 8.9. C34H35ClNP2RhS2 requires C,
56.6; H, 4.9; N, 1.9; S, 8.9%). wmax/cm−1 (Nujol) 570
(PS), 1145 and 805 (P2N). lH (CDCl3) 1.38 (s, 30 H,
C5Me5), 6.90–8.20 (m, 20 H, Ph). lP (CDCl3) 36.45 (s).
Complex 6: yield, 165 mg, 78% (Found: C, 49.9; H, 4.4;
N, 1.8. C34H35ClNP2RhSe2 requires C, 50.1; H, 4.3; N,
1.7%). wmax/cm−1 (Nujol) 535 (PSe), 1165 and 785
(P2N). lH (CDCl3) 1.39 (s, 30 H, C5Me5), 7.20–7.95 (m,
20 H, Ph). lP (CDCl3) 24.9 (s, 1J(PSe)=570 Hz).
Complex 7: yield, 145 mg, 67% (Found: C, 50.1; H, 4.5;
N, 1.7; S, 7.4. C34H35ClIrNP2S2 requires C, 50.3; H, 4.4;
N, 1.7; S, 7.9%). wmax/cm−1 (Nujol) 560 (PS), 1165 and
800 (P2N). lH (CDCl3) 1.36 (s, 30 H, C5Me5), 7.04–8.20
3
(P2N). lH (CDCl3) 1.07 [d, 6 H, Me(iPr), J(HH)=5.8
Hz], 1.88 (s, 3 H, Me), 2.73 [m, 1 H, CH(iPr)], 4.75 and
4.90 [4 H, AB system, J(HH)=4.6 Hz], 6.96–8.24 (m,
1
20 H, Ph). lP (CDCl3) 29.4 [s, J(PSe)=563 Hz].
2.1.6. [(p5-C5Me5)M{p2-(EPPh2)2N}(PPh3)]PF6
(M=Rh; E=S (13), Se (14). M=Ir; E=S (15), Se
(16))
The complexes can be alternatively prepared by the
two methods described below.

6
M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
(i) To a solution of complexes 5–8 (0.1 mmol) in
2.1.7. [(p6-C6Me6)Ru{p2-(EPPh2)2N}(C5H5N)]BF4
(E=S (17), Se (18))
CH2Cl2 (20 cm3) the stoichiometric amount of AgPF6
(25.8 mg; 0.1 mmol) in Me2CO (10 cm3) was added.
The mixture was boiled under reflux for 4 h. The AgCl
formed was filtered off through Kieselguhr and PPh3
(26.3 mg; 0.1 mmol) was added to the obtained solu-
tion. The resulting solution was stirred for 1 h, concen-
trated to a small volume and the addition of diethyl
ether caused the precipitation of the compounds. Re-
crystallisation from acetone–diethyl ether led to orange
crystals.
To a solution of the dinuclear complex [{(h6-
C6Me6)RuCl}2(m-Cl)2] (66.9 mg; 0.1 mmol) in CH2Cl2
(20 cm3) was added AgBF4 (79.4 mg; 0.4 mmol) in
Me2CO (10 cm3). The mixture was boiled under reflux
for 2 h. The AgCl formed was filtered off through
Kieselguhr and to the obtained solution NH(EPPh2)2
(0.2 mmol; E=S (90 mg), Se (108 mg)) and C5H5N (16
ml, 0.2 mmol) were added. After stirring for 1 h, the
solution was concentrated under reduced pressure to a
small volume and the complexes crystallised by addi-
tion of diethyl ether. Orange–red crystals were ob-
tained from acetone–diethyl ether. Complex 17: yield,
81 mg, 46% (Found: C, 55.7; H, 5.0; N, 3.1; S, 6.9.
C41H43BF4N2P2RuS2 requires C, 56.1; H, 4.9; N, 3.2; S,
6.6%). wmax/cm−1 (KBr) 568 (PS), 1176 and 798 (P2N),
1100 and 514 (BF4−). lH (CDCl3) 1.81 (s, 18 H, C6Me6),
7.20–7.80 (m, 20 H, Ph), 6.81 (t, C5H5N), 8.38 (d,
C5H5N). lP (CDCl3) 24.1 (s). Complex 18: yield, 93 mg,
48% (Found: C, 49.9; H, 4.4; N, 2.8.
C41H43BF4N2P2RuSe2 requires C, 50.8; H, 4.5; N,
2.9%). wmax/cm−1 (KBr) 505 (PSe), 1178 and 786 (P2N),
1100 and 539 (BF4−). lH (CDCl3) 1.83 (s, 18 H, C6Me6),
7.21–7.90 (m, 20 H, Ph), 6.77 (t, C5H5N), 8.40 (d,
(ii) To a solution of the dinuclear complex [{(h5-
C5Me5)MCl}2(m-Cl)2] (0.1 mmol; Rh (62 mg), Ir (80
mg)) in CH2Cl2 (20 cm3) was added AgPF6 (103.2 mg;
0.4 mmol) in Me2CO (10 cm3). The mixture was boiled
under reflux for 2 h. The AgCl formed was filtered off
through Kieselguhr and to the obtained solution
NH(EPPh2)2 (0.2 mmol; E=S (90 mg), Se (108 mg))
and PPh3 (52.6 mg; 0.2 mmol) were added. After stir-
ring for 1 h, the solution was evaporated to dryness, the
residue extracted with the minimal amount of CH2Cl2
and the solution chromatographed on neutral Al2O3
(90% activity) using CH2Cl2 as eluent. The obtained
solution was concentrated under reduced pressure to a
small volume and the complexes crystallised by addi-
tion of diethyl ether.
1
C5H5N). lP (CDCl3) 20.9 [s, J(PSe)=576 Hz].
Method (i). Complex 13: yield, 59 mg, 54% (Found:
C, 56.6; H, 4.5; N, 1.2; S, 5.6. C52H50F6NP4RhS2
requires C, 57.1; H, 4.6; N, 1.3; S, 5.9%). wmax/cm−1
(KBr) 525 (PS), 1177 and 798 (P2N), 840 and 565
(PF−6 ). lH (CDCl3) 1.18 [d, 30 H, C5Me5, 4J(PAH)=3.5
Hz)], 6.83–8.16 (m, 20 H, Ph). lP (CDCl3) 30.3 [dt,
1J(RhPA)=134 Hz, 3J(PBPA)=17 Hz], 31.5 [d, PB]
2.2. Crystal structure determination of
[(p5-C5Me5)RhCl{p2-(SePPh2)2N}] (6) and
[(p5-C5Me5)IrCl{p2-(SePPh2)2N}] (8)
Suitable crystals for the X-ray analyses were obtained
by slow diffusion of diethyl ether into acetone solutions
of complexes 6 and 8. Crystal data and refinement
parameters are summarised in Table 1. Data were
collected on a Siemens–Stoe AED-2 (6) or on a
Siemens P4 (8) diffractometer with graphite-monochro-
mated Mo–Ka radiation, using the ꢀ–2q scan method.
Three standard reflections were monitored every 55 min
(6) or every 97 measured reflections (8) throughout data
collection; no significant variations were observed. All
data were corrected for Lorentz and polarisation ef-
fects, and for absorption using a semiempirical method
(„ scan) [12]; minimum and maximum transmission
factors are listed in Table 1. All structures were solved
by Patterson method and Fourier techniques, and
1
−145.0 [sp, PF−6 , J(PF)=714 Hz]. Complex 14: yield,
60 mg, 51% (Found: C, 53.4; H, 4.1; N, 1.1.
C52H50F6NP4RhSe2 requires C, 52.8; H, 4.3; N, 1.2%).
wmax/cm−1 (KBr) 509 (PSe), 1196 and 789 (P2N), 839
and 558 (PF−6 ). lH (CDCl3) 1.30 [d, 30 H, C5Me5,
4J(PAH)=3.6 Hz)], 6.80–8.10 (m, 20 H, Ph). lP
(CDCl3) 32.1 [dt, 1J(RhPA)=140 Hz, 3J(PBPA)=17
1
Hz], 20.1 [d, PB, J(PBSe)=566 Hz], −145.0 [sp, PF−6 ,
1J(PF)=714 Hz]. Complex 15: yield, 67 mg, 56%
(Found: C, 52.2; H, 4.3; N, 1.2; S, 5.2.
C52H50F6IrNP4S2 requires C, 52.6; H, 4.2; N, 1.2; S,
5.4%). wmax/cm−1 (KBr) 530 (PS), 1175 and 805 (P2N),
840 and 564 (PF−6 ). lH (CDCl3) 1.20 [d, 30 H, C5Me5,
4J(PAH)=2.5 Hz], 6.83–8.14 (m, 20 H, Ph). lP
(CDCl3) −2.95 [t, 3J(PBPA)=19 Hz], 25.6 [d, PB],
refined by full-matrix least squares on F2
(SHELXL-
1
−145.0 [sp, PF−6 , J(PF)=714 Hz]. Complex 16: yield,
97) [13]. Absolute structure was checked in both cases
using the Flack parameter (x= −0.013(10) 6 and
−0.018(12) 8) [14]. The function minimised was
63 mg, 49% (Found: C, 48.9; H, 3.9; N, 1.1.
C52H50F6IrNP4Se2 requires C, 48.9; H, 4.0; N, 1.1%).
wmax/cm−1 (KBr). lH (CDCl3) 1.31 [d, 30 H, C5Me5,
4J(PAH)=2.2 Hz], 6.83–8.03 (m, 20 H, Ph). lP
(CDCl3) −2.3 [t, 3J(PBPA)=19 Hz], 25.6 [d, PB,
1J(PBSe)=558 Hz], −145.0 [sp, PF−6 , 1J(PF)=714
Hz].
S[w(F2o−F2c)2] with the weight defined as w−1
=
[|2(Fo2)+(xP)2+yP] where P=(Fo2 +2F2c)/3. Atomic
scattering factors, corrected for anomalous dispersion,
were used as implemented in the refinement program
[13].

M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
7
2.2.1. Complex 6
with weight parameters x=0.0391 and y=6.6804. The
Anisotropic displacement parameters were used in
the last cycles of refinement for all non-hydrogen
atoms. The hydrogen atoms of the pentamethylcy-
clopentadienyl methyl groups were included in calcu-
lated positions; all the remaining ones were obtained
from difference Fourier maps. All the hydrogens were
refined riding on carbon atoms with two common
displacement parameters (phenyl and methyl groups).
The refinement converged to R(F)=0.0464 [F2\
2|(F2)] and wR(F2)=0.1010 (all data), with weight
parameters x=0.0427 and y=1.8372. Residual peaks
highest residual peaks in the final difference map, lower
than 1.136 e A−3, were situated close to the metal
,
centre.
3. Results and discussion
The dinuclear complexes [{(hn-ring)MCl}2(m-Cl)2] re-
acted in dichloromethane–acetone with silver salts AgA
of non-coordinating anions (A=PF−6 , BF4−) in a 1:2
molar ratio, to form silver chloride and, most probably,
the solvate complex [(hn-ring)MCl(solvent)2]+, which
further reacted with NH(PPh2)2 to give cationic com-
pounds of the type [(hn-ring)MCl{h2-(PPh2)2NH}]A
[(hn-ring)M=(h5-C5Me5)Rh; A=PF6− (1a), BF4− (1b).
(hn-ring)M=(h5-C5Me5)Ir; A=PF6− (2a), BF4− (2b).
(hn-ring)M=(h6-p-MeC6H4i Pr)Ru; A=BF−4 (3). (hn-
ring)M=(h6-C6Me6)Ru; A=PF−6 (4)]. Complexes 1–4
were isolated as stable microcrystalline solids and char-
acterised by elemental analyses, IR and NMR spec-
troscopy. The IR spectra showed the presence of the
uncoordinated anion (PF−6 : ca. 840, 560 cm−1; BF4−:
ca. 1050, 510 cm−1) together with a broad absorption
band, in the 3423–3443 cm−1 region, corresponding to
in the final difference map were in the range 0.662 and
−3
,
−0.637 e A
.
2.2.2. Complex 8
After refinement of all non-hydrogen atoms with
anisotropic displacement parameters, the hydrogen
atoms of the pentamethylcyclopentadienyl ligand and
some of the phenyl groups were included in calculated
positions; the remaining ones were obtained from dif-
ference Fourier maps. All the hydrogens were refined
riding on carbon atoms with two common thermal
parameters, one for phenyl groups and another for
methyl groups. The refinement converged to R(F)=
0.0411 [F2\2|(F2)] and wR(F2)=0.0993 (all data),
1
the NꢀH bond. The H-NMR spectra of complexes 1a
and 2a, in deuterated chloroform, exhibited a singlet
resonance at l 1.49 (1a) or 1.53 ppm (2a) attributed to
the C5Me5 group and two multiplets in the 7.24–7.59
ppm region corresponding to the phenyl protons of the
phosphine ligand. For complex 2a, the NH amine
proton was observed as a broad singlet centred at l 8.8
ppm. The 31P-NMR spectra of complexes 1a and 2a
showed a doublet resonance at l 48.5 ppm with a
1J(RhP) coupling of 118.5 Hz and a singlet at l 16.8
ppm, respectively.
Table 1
Crystallographic data and refinement details for [(h5-C5Me5)MCl{h2-
(SePPh2)2N}] (M=Rh (6), Ir (8))
6
8
Crystal colour, habit
Dark red, prismatic Red, block
block
Crystal size (mm)
Formula
0.40×0.34×0.23
C34H35ClNP2RhSe2 C34H35ClIrNP2Se2
0.33×0.24×0.18
1
Analogously, the H-NMR spectra of compounds 3
M
815.85
905.14
and 4 showed the presence of the arene and NH(PPh2)2
Crystal system
Space group
T (K)
Orthorhombic
P212121 (no. 19)
293(2)
Orthorhombic
P212121 (no. 19)
293(2)
resonances in the required proportions. In particular, a
2
triplet centred at l 5.41 ppm with a J(PH) coupling
,
a (A)
8.9245(7)
17.7607(13)
20.575(3)
3261.2(6)
4
2.961
1.51–27.53
9425
8.931(2)
constant of 4.65 Hz denoted the presence of the NH
functionality in the (p-MeC6Hi4Pr)Ru compound 3. The
31P-NMR spectra of the cations consisted of a singlet at
60.7 or 58.4 ppm for 3 and 4, respectively.
,
b (A)
17.740(4)
20.627(4)
3268.1(12)
4
6.518
1.51–25.02
8194
5740
(Rint=0.0479)
0.222, 0.387
,
c (A)
3
,
V/ (A )
Z
v(mm−1
)
On the other hand, the reactions of the starting
dinuclear complexes [{(hn-ring)MCl}2(m-Cl)2] with the
chalcogenide ligands NH(EPPh2)2 (E=S, Se) in
dichloromethane–acetone, in the presence of silver hex-
afluorophosphate or tetrafluoroborate, yielded neutral
complexes of the general formula [(hn-ring)MCl{h2-
(EPPh2)2N}] [(hn-ring)M=(h5-C5Me5)Rh; E=S (5), Se
(6). (hn-ring)M=(h5-C5Me5)Ir; E=S (7), Se (8). (hn-
ring)M=(h6-C6H6)Ru, E=S (9). (hn-ring)M=(h6-p-
MeC6Hi4Pr)Ru, E=S (10). (hn-ring)M=(h6-C6Me6)-
Ru, E=Se (11). (hn-ring)M=(h6-p-MeC6Hi4Pr)Ru,
E=Se (12)]. The spontaneous loss of hydrogen hexa-
q Range (°)
No. collected reflections
No. unique reflections
7518
(Rint=0.0275)
0.384, 0.549
Min., max. transmission
factors
Data/restraints/parameters 7518/0/377
5740/0/377
0.0411
0.0993
R(F) [F2\2|(F2)] a
wR(F2) (all data) b
0.0464
0.1010
a R(F)=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ for 6116 and 4913 observed reflections,
respectively.
b Rw(F2)=[Sw(Fo2−F2c)2/Sw(F2o)2]1/2
.

8
M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
fluorophosphate or tetrafluoroborate confirmed that
the acidity of the amine proton of the chalcogenide
ligands was enhanced by coordination and, as expected,
is higher than that of the amine proton in the dppa
ligand. The neutral complexes were isolated as micro-
crystalline solids. In all cases their IR spectra in Nujol
mulls showed the absorption bands corresponding to
P2N and PꢁE groups. The w(PS) and w(PSe) stretching
bands were shifted to lower frequencies (w(PS)=550–
570 cm−1 and w(PSe)=530–535 cm−1) relative to that
of the free neutral ligand (w(PS)=625 cm−1 and
w(PSe)=546 cm−1) [4b,15], as a consequence of the
decrease in the bond order. The wasym(P2N) bands of the
dithioimidophosphinate complexes 5, 7, 9, and 10 are in
the ranges 1145–1180 and 795–805 cm−1 (935 and 932
cm−1 in the free ligand) and those of the diselenoimi-
dophosphinates 6, 8, 11, and 12 in the ranges 1150–
1180 and 780–785 cm−1 (1114 and 781 cm−1 in the
free ligand) [16], reflecting the increase in the PꢀN bond
order. The mass spectrum of complex 8 (FAB+ mode)
showed a peak at m/z 905, with an isotopic distribution
that matched the calculated for the proposed neutral
formulation.
difference in the chemical shift for the phosphorus
nucleus of the PPh3 ligand between the rhodium and
the iridium compounds (about 34 ppm) reflects the
softer character of the iridium atom.
Attempts to obtain similar cationic areneꢀruthenium
complexes, through the abstraction of the chloride lig-
and on complexes 9–12 with silver salts and subsequent
reaction with triphenylphophine, were unsuccessful. In
all cases, the reaction gave rise to a mixture of unchar-
acterised solids. However, the reactions of the solvate
intermediate complex [(h6-C6Me6)Ru(solvent)3]2+ with
the appropriate chalcogenide ligands and a stronger
s-donor ligand such as pyridine, yielded the corre-
sponding cationic derivatives [(h6-C6Me6)Ru{h2-
(EPPh2)2N}(NC5H5)]+ which were isolated as
tetrafluoroborate salts (E=S (17), Se (18)). The 1H-
NMR spectra showed a singlet for the C6Me6 protons
together with a triplet and a doublet corresponding to
the pyridine ligand. The expected additional triplet for
the pyridine protons is masked by two broad multiplets
attributable to the phenyl groups of the chalcogenide
ligands. Their 31P-NMR spectra consisted of one singlet
with the expected PꢀSe coupling (576 Hz) for complex
18.
The 1H-NMR spectra of complexes 5–12 were in
good agreement with the proposed formulations show-
ing the expected resonances of the C5Me5 or arene
coordinated rings and the phenyl groups of the chalco-
genide ligands in the required proportions (see Section
2). Their 31P-NMR spectra exhibited a single resonance
in the range l 18.4–32.6 ppm, with the expected phos-
phorusꢀselenium coupling for the diselenoimidophos-
phinate complexes ranging between 563 and 578 Hz.
Complexes 5–8 reacted with silver hexafluorophos-
phate in refluxing dichloromethane–acetone leading to
the cationic solvate intermediate [(h5-C5Me5)M{h2-
(EPPh2)2N}(solvent)]+, which in turn reacted with
triphenylphosphine to yield the cationic complexes [(h5-
C5Me5)M{h2-(EPPh2)2N}(PPh3)]PF6 (M=Rh; E=S
(13), Se (14). M=Ir; E=S (15), Se (16)). Similar
results were obtained by treatment of the intermediate
solvate complex [(h5-C5Me5)M(solvent)3]2+, prepared
from [{(h5-C5Me5)MCl}2(m-Cl)2] and AgPF6, with
equimolar amounts of NH(EPPh2)2 and PPh3.
All cationic compounds 13–18 were isolated as stable
microcrystalline solids. Their IR spectra showed the
characteristic bands of the PE and P2N bonds, the
coordinated ligands PPh3 and C5H5N, together with the
bands corresponding to the uncoordinated anion.
3.1. X-ray crystal structures of
[(p5-C5Me5)RhCl{p2-(SePPh2)2N}] (6) and
[(p5-C5Me5)IrCl{p2-(SePPh2)2N}] (8)
Although the spectroscopic data in the solid state
and in solution suggest the loss of the aminic proton of
the chalcogenide ligands upon coordination, two analy-
ses by X-ray diffraction methods were carried out to
establish the molecular structures and to obtain addi-
tional information on bonding parameters. Figs. 1 and
2 display the molecular representation of complexes 6
and 8, respectively. Table 2 collects selected bond dis-
tances and angles for both structures.
From a crystallographic point of view, both crystal
structures are isostructural, packed in the same space
group and with comparable cell parameters. At a
molecular level, both metal complexes are also rather
similar; although some of the molecular parameters
(bond lengths and angles) are statistically different,
none of them evince a significant diversity that could be
potentially associated with chemical distinctions. Both
metal centres exhibit highly distorted pseudo-octahedral
environments with the pentamethylcyclopentadienyl
group occupying three formal coordination sites, with
the chelating tetraphenyldiselenoimidodiphosphinate
ligand bonded to the metal through two selenium
1
The H-NMR spectra of complexes 13–16 showed
the expected doublet for the C5Me5 groups due to
PAꢀH coupling (PAPh3) and the 31P-NMR spectra of
the rhodium complexes 13 and 14 exhibited a doublet
of triplets (PA) and a doublet (PB), due to RhꢀPA and
PAꢀPB couplings [N(EPBPh2)2] centred at l 30.3 and
31.5 ppm and at l 32.05 and 20.1 ppm, respectively.
The spectrum of complex 14 presents, moreover, the
corresponding PꢀSe coupling. The 31P-NMR spectra of
the iridium complexes 15 and 16 consisted of a triplet
and a doublet assigned to PA and PB nuclei, centred at
l −2.95 and 25.6 ppm and at −2.3 and 25.6 ppm,
respectively, with a PAꢀPB coupling of 19 Hz. The

M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
9
slightly longer than the distances observed in analogous
cationic complexes containing the ‘(h5-C5Me5)M’ moi-
ety, such as in [(h5-C5Me5)RhCl(prophos)]BF4
5
,
(2.393(1)A) [19], [(h -C5Me5)RhCl(phen)]ClO4 (2.386(1)
5
2
,
A) [20] or in [(h -C5Me5)IrCl{h -Ph2PCH2SPh}]BF4
5
,
(2.381(2) A) [18a] and [(h -C5Me5)IrCl{L-histidine]
,
(2.402(5) A) [21].
In both structures, the MSe2P2N six-membered rings
adopt analogous puckered conformations. This pucker-
ing twists the metallacycles towards a slightly distorted
boat conformation, with a selenium and a phosphorus
,
atom at the stern and bow of the boat (Q=0.909(2) A,
,
q=82.8(2) and ƒ=69.2(2)° 6; Q=0.927(3) A, q=
81.5(3) and ƒ=67.6(4)° 8) [22]. Within both metallacy-
cles, none of the bond distances or angles reflect any
structural or chemical difference. The RhꢀSe bond dis-
,
tances (2.5317 and 2.5266(8) A) are slightly shorter
than those found in the closely related cationic complex
Table 2
Fig. 1. Molecular diagram of the complex [(h5-C5Me5)RhCl{h2-
(SePPh2)2N}] (6), together with the numbering scheme used.
5
,
Selected bond distances (A) and angles (°) for complexes [(h -
C5Me5)MCl{h2-(SePPh2)2N}] (M=Rh (6), Ir (8))
6 (M=Rh)
8 (M=Ir)
MꢀCl
2.4366(17)
2.5317(8)
2.5266(8)
1.804(7)
2.175(6)
2.158(6)
2.177(6)
2.170(6)
2.195(7)
2.1693(16)
2.1771(16)
1.594(5)
1.597(5)
2.447(3)
MꢀSe(1)
MꢀSe(2)
MꢀG a
2.5361(11)
2.5396(11)
1.811(11)
2.190(10)
2.188(11)
2.175(11)
2.202(11)
2.176(10)
2.199(3)
MꢀC(1)
MꢀC(2)
MꢀC(3)
MꢀC(4)
MꢀC(5)
Se(1)ꢀP(1)
Se(2)ꢀP(2)
P(1)ꢀN
2.184(3)
1.601(7)
1.596(8)
P(2)ꢀN
ClꢀMꢀSe(1)
95.93(5)
86.26(5)
120.2(2)
96.65(3)
120.5(2)
128.5(2)
111.43(5)
109.17(5)
127.7(3)
118.08(19)
111.2(2)
105.86(19)
111.9(3)
104.8(3)
103.5(3)
117.43(19)
105.2(2)
112.4(2)
106.0(3)
107.4(3)
107.8(3)
85.43(8)
93.70(7)
120.7(4)
96.46(4)
128.7(3)
121.8(3)
108.57(8)
111.77(8)
128.1(5)
117.1(3)
104.7(3)
112.4(3)
106.1(4)
107.5(5)
108.6(4)
117.9(3)
111.4(4)
106.6(3)
111.7(5)
104.6(4)
103.1(5)
ClꢀMꢀSe(2)
ClꢀMꢀG a
Se(1)ꢀMꢀSe(2)
Se(1)ꢀMꢀG a
Se(2)ꢀMꢀG a
MꢀSe(1)ꢀP(1)
MꢀSe(2)ꢀP(2)
P(1)ꢀNꢀP(2)
Se(1)ꢀP(1)ꢀN
Se(1)ꢀP(1)ꢀC(11)
Se(1)ꢀP(1)ꢀC(17)
NꢀP(1)ꢀC(11)
NꢀP(1)ꢀC(17)
C(11)ꢀP(1)ꢀC(17)
Se(2)ꢀP(2)ꢀN
Se(2)ꢀP(2)ꢀC(23)
Se(2)ꢀP(2)ꢀC(29)
NꢀP(2)ꢀC(23)
NꢀP(2)ꢀC(29)
C(23)ꢀP(2)ꢀC(29)
Fig. 2. Molecular representation of the neutral complex [(h5-
C5Me5)IrCl{h2-(SePPh2)2N}] (8), with the labelling scheme used.
atoms, and with a chloride atom completing the coordi-
nation sphere.
,
The two MꢀG (C5Me5 centroid) distances, 1.804(7) A
,
,
in 6 (RhꢀC range 2.158(6)–2.195(7) A) and 1.811(11) A
,
for complex 8 (IrꢀC range 2.175(11)–2.202(11) A), are
identical within the experimental error and compare
well with the values found in related pentamethylcy-
clopentadienyl rhodium(III) [17] and iridium(III) [18]
,
a G represents the centroid of the pentamethylcyclopentadienyl
ring.
complexes. The RhꢀCl (2.4366(17) A) and IrꢀCl
,
(2.447(3) A) bond lengths are also very similar, but are

10
M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
[(h5-C5Me5)Rh{h3-(SePPh2)2CH}]ClO4 (mean 2.563(1)
Cooperacio´n Iberoamericano, Spain, for financial sup-
port. S.E. thanks the DGICYT for a grant.
,
A) [18b] but longer than those found in selenolato or
selenido complexes such as [(h5-C5H5)Rh(h2-C,Se-
i
5
,
CH3CH2Se)(P Pr3)] (average 2.461(1) A) [23], or [{(h -
,
C5Me5)Rh(m3-Se)}4] (mean 2.459(1) A) [24]. In the case
References
of complex 8, the IrꢀSe bond lengths (2.5361 and
[1] (a) P. Bhattacharyya, J.D. Woollins, Polyhedron 14 (1995) 3367.
(b) A. Laguna, M. Laguna, J. Organomet. Chem. 394 (1990)
3367. (c) C.S. Browning, D.H. Farrar, D.C. Frankel, J.J. Vittal,
Inorg. Chim. Acta 254 (1997) 329.
[2] I. Haiduc, R. Cea-Olivares, S. Herna´ndez-Ortega, C. Silvestru,
Polyhedron 14 (1995) 2041.
[3] J.D. Woollins, J. Chem. Soc. Dalton Trans. (1996) 2893.
[4] (a) N. Zu´n˜iga-Villarreal, C. Silvestru, M. Reyes, S. Herna´ndez-
Ortega, C. Alvarez, J. Organomet. Chem. 496 (1995) 169. (b) P.
Bhattacharyya, A.M. Slawin, D.J. Williams, J.D. Woollins, J.
Chem. Soc. Dalton Trans. (1995) 2489.
,
2.5396(11) A) compare well with the distances observed
in the Ir(III) diselenium complex [Ir(Se2)(dppe)2]Cl
,
(2.534(2) A) [25], but are also longer than those found
in the tetraselenido derivative [(h5-C5Me5)Ir(h2-
,
Se4)(PMe3)] (mean 2.469(1) A) [26].
Interestingly, the PꢀSe bond distances (2.1771 and
,
,
2.1693(16) A, 6, and 2.199(3) and 2.184(3) A, 8) show a
significant lengthening if compared with the values
,
found in the neutral free ligand (average 2.093(1) A).
Additionally, the PꢀN bond lengths (1.597(5) and
[5] A. Laguna, M. Laguna, A. Rojo, M.N. Fraile, J. Organomet.
Chem. 315 (1986) 269.
[6] I. Haiduc, I. Silaghi-Dumitrescu, Coord. Chem. Rev. 74 (1986)
127.
,
,
1.594(5) A in 6; 1.601(7) and 1.596(8) A in 8) are
markedly shorter than in free ligand (average 1.682(3)
,
A) [27]. This structural behaviour has also been re-
[7] Recently, M.B. Smith et al. (J. Chem. Soc. Dalton Trans. (1998)
2467) have reported the synthesis of neutral complexes [(h5-
C5Me5)RhCl{h2-(EPPh2)2N}] and [(h6-p-MeC6Hi4Pr)RuCl{h2-
(EPPh2)2N}] (E=S, Se) by reaction of the corresponding
ported for this bidentate anionic ligand in the related
bis-homoleptic compounds [Sn{(SePPh2)2N}2] (PꢀSe
,
average 2.175(6)A) [28] and [Pd{(SePPh2)2N}2] (means:
,
,
PꢀSe 2.184(3) A; PꢀN 1.591(11) A) [27], or in the
starting
dinuclear
complex
[(hn-ring)MCl(m-Cl)]2
with
related Pd(II) complex [Pd(C9H12N){(SePPh2)2N}2]
K[(Ph2PSe)2N] in THF.
,
(2.184(2) and 1.598(5) A) [27], and evidences some
[8] P.M. Maitlis, Acc. Chem. Res. 1 (1978) 301.
[9] R.H. Zelonka, M.C. Baird, Can. J. Chem. 50 (1972) 3063.
degree of p-delocalisation over the six-membered ring
MSe2P2N. In fact the PꢀN bond distances observed in 6
and 8 are markedly longer than the mean length re-
[10] M.A. Bennett, A.K. Smith, J. Chem. Soc. Dalton Trans. (1974)
233.
[11] F.T. Wang, J. Najdzionek, K.L. Leneker, H. Wasserman, D.M.
Braitsch, Synth. React. Inorg. Met-Org. Chem. 8 (1978) 119.
[12] A.C.T. North, D.C. Phillips, F.S. Mathews, Acta Crystallogr.
Sect. A 24 (1968) 351.
,
ported for PꢁN double bonds (1.540(22) A) [29] in
coordinated iminophosphines and are similar to those
showed in tetrameric cyclophosphazene [(Ph2PN)4] (av-
[13] G.M. Sheldrick, SHELXL-97 Program for Crystal Structure
Refinement, University of Go¨ttingen, Germany, 1997.
[14] H.D. Flack, Acta Crystallogr. Sect. A 39 (1983) 876.
[15] A. Schmidpeter, H. Groeger, Z. Anorg. Allg. Chem. 345 (1966)
106.
,
erage 1.590(3) A) [30]. The values of the PꢀNꢀP bond
angles in 6 (127.7(3)°) and 8 (128.1(5)°) are reduced
respect to the neutral ligand (132.3(2)°) [27] and are
slightly larger than those found in the square-planar
platinum and palladium complexes [M{(SePPh2)2N}2]
(Pt, 123.3(5)°; Pd, 122.9.(5)°) [27]. The bond angles at
selenium and phosphorus atoms are similar to those
reported for the coordinated ligand in the above men-
tioned homoleptic complexes [27,28].
[16] D.J. Williams, A.M.Z. Slawin, J.R. Phillips, J.D. Woollins,
Polyhedron 13 (1996) 3175.
[17] See for instance: (a) D. Carmona, C. Cativiela, R. Garc´ıa-Cor-
reas, F.J. Lahoz, M.P. Lamata, J.A. Lo´pez, M.P. Lo´pez-Ram de
Viu, L.A. Oro, E. San Jose´, F. Viguri, J. Chem. Soc. Chem.
Commun. (1996) 1247. (b) M. Valderrama, R. Contreras, M.
Bascun˜a´n, D. Boys, Polyhedron 13 (1994) 1101. (c) M.T. Pinil-
los, M.P. Jarauta, D. Carmona, L.A. Oro, M.C. Apreda, C.
Foces-Foces, F.H. Cano, J. Organomet. Chem. 345 (1988) C13.
(d) M.T. Pinillos, M.P. Jarauta, D. Carmona, L.A. Oro, M.C.
Apreda, C. Foces-Foces, F.H. Cano, J. Chem. Soc. Dalton
Trans. (1989) 1987.
[18] See for instance: (a) M. Valderrama, R. Contreras, D. Boys,
Polyhedron 16 (1997) 1811. (b) M. Valderrama, R. Contreras, V.
Arancibia, P. Mun˜oz, D. Boys, M.P. Lamata, F. Viguri, D.
Carmona, F.J. Lahoz, J.A. Lo´pez, L.A. Oro, J. Organomet.
Chem. 545 (1997) 507. (c) M. Valderrama, R. Contreras,
J. Organomet. Chem. 513 (1996) 7. (d) M. Valderrama, J.
Cuevas, D. Boys, D. Carmona, M.P. Lamata, F. Viguri, R.
Atencio, F.J. Lahoz, L.A. Oro, J. Chem. Soc. Dalton Trans.
(1996) 2877.
4. Supplementary material
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC reference numbers 137547 and
137548 for compounds 6 and 8, respectively. See http://
www.rsc.org/suppdata/dt/for crystallographic files in
.cif format.
Acknowledgements
[19] D. Carmona, F.J. Lahoz, L.A. Oro, M.P. Lamata, F. Viguri, E.
San Jose´, Organometallics 15 (1996) 2961.
[20] M.T. Youinou, R. Ziessel, J. Organomet. Chem. 363 (1989) 197.
We thank the Fondo de Desarrollo Cient´ıfico y Tec-
nolo´gico, Chile (Grant 8980007) and the Instituto de

M. Valderrama et al. / Journal of Organometallic Chemistry 607 (2000) 3–11
11
[21] P. Kramer, K. Polborn, H. Wanjek, I. Zahn, M. Beck, Chem.
Ber. 123 (1990) 767.
[22] D. Cremer, J.A. Pople, J. Am. Chem. Soc. 97 (1975)
1354.
[23] H. Werner, H. Paul, W. Knaup, J. Wolf, G. Mu¨ller, J. Riede, J.
Organomet. Chem. 358 (1988) 95.
[24] S. Schulz, M. Andruh, T. Pape, T. Heinze, H.W. Roesky, L.
Haming, A. Kuhn, Organometallics 13 (1994) 4004.
[25] (a) A.P. Ginsberg, J.H. Osborne, C.E. Sprinkle, Inorg. Chem. 22
(1983) 1781. (b) A.P. Ginsberg, W.E. Lindsell, C.R. Sprinkle, W.
West, R.L. Cohen, Inorg. Chem. 21 (1982) 3666.
[26] M. Herberhold, G.-X. Jin, A.L. Rheingold, Chem. Ber. 124
(1991) 2245.
[27] P. Bhattacharyya, J. Novosad, J. Phillips, A.M.Z. Slawin, D.A.
Williams, J.D. Woollins, J. Chem. Soc. Dalton Trans. (1995)
1607.
[28] (a) R. Cea-Olivares, J. Novosad, J.D. Woollins, A.M.Z. Slawin,
V. Garc´ıa-Montalvo, G. Espinosa-Pe´rez, P. Garc´ıa, J. Chem.
Soc. Chem. Commun. (1996) 519. (b) V. Garc´ıa-Montalvo, J.
Novosad, P. Kilian, J.D. Woollins, A.M.Z. Slawin, P. Garc´ıa,
M. Lo´pez-Cardoso, G. Espinosa-Pe´rez, R. Cea-Olivares, J.
Chem. Soc. Dalton Trans. (1997) 1025.
[29] A.G. Orpen, L. Brammer, F.H. Allen, O. Kennard, D.G. Wat-
son, R. Taylor, J. Chem. Soc. Dalton Trans. (1989) S1.
[30] M.J. Begley, D.B. Sowerby, R.J. Tillot, J. Chem. Soc. Dalton
Trans. (1974) 2527.
.