Synthesis of transition-metal complexes with heterodifunctional ligands derived of NH(PPh2)2. Crystal structure of [(η5-C5Me5)RhCl{η 2-P,Se-Ph2PNP(Se)Ph2}]·CH 2Cl2

Article abstract of DOI:10.1016/S0022-328X(01)01081-6

The uncoordinated P atom of the bis(diphenylphosphine)amine (dppa) ligand in complexes [(ring)MCl₂(η¹-P-PPh₂NHPPh₂)] (M=Rh, Ir, Ru) reacts with sulphur or selenium to form [(ring)MCl₂(η¹-P-PPh₂NHP(E)Ph₂)] (E=S (1-3), Se (4-6)) containing the P-coordinated monosulphide or monoselenide ligands. The selenium derivatives have also been directly prepared from the corresponding [{(ring)MCl₂}₂] dimer and dppaSe. Chloride abstraction from rhodium and ruthenium complexes gives the neutral compounds [(ring)MCl(η²-P,E-PPh₂NP(E)Ph₂)] (7-10) whilst the iridium derivatives yield cationic complexes of the general formula [{η⁵-C₅Me₅)IrCl(η ²-P,E-PPh₂NHP(E)Ph₂)]⁺ (11 and 12). The crystal structure of complex [(η⁵-C₅Me₅)RhCl{η ²-P,Se-PPh₂NP(Se)Ph₂}] has been established by X-ray crystallography. The rhodium atom exhibits a distorted octahedral coordination with a η⁵-C₅Me₅ group occupying the centre of three octahedral sites; a bidentate chelate P,Se-bonded ligand and a chloride atom complete the metal coordination sphere.

Full text of DOI:10.1016/S0022-328X(01)01081-6

Journal of Organometallic Chemistry 633 (2001) 182–188
www.elsevier.com/locate/jorganchem
Synthesis of transition-metal complexes with heterodifunctional
ligands derived of NH(PPh2)2. Crystal structure of
[(h5-C5Me5)RhCl{h2-P,Se-Ph2PNP(Se)Ph2}]·CH2Cl2
Mauricio Valderrama a,*, Rau´l Contreras a, Patricio Mun˜oz a, M. Pilar Lamata 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 May 2001; accepted 20 June 2001
Abstract
The uncoordinated P atom of the bis(diphenylphosphine)amine (dppa) ligand in complexes [(ring)MCl2(h1-P-PPh2NHPPh2)]
(M=Rh, Ir, Ru) reacts with sulphur or selenium to form [(ring)MCl2(h1-P-PPh2NHP(E)Ph2)] (E=S (1–3), Se (4–6)) containing
the P-coordinated monosulphide or monoselenide ligands. The selenium derivatives have also been directly prepared from the
corresponding [{(ring)MCl2}2] dimer and dppaSe. Chloride abstraction from rhodium and ruthenium complexes gives the neutral
compounds [(ring)MCl(h2-P,E-PPh2NP(E)Ph2)] (7–10) whilst the iridium derivatives yield cationic complexes of the general
formula [{h5-C5Me5)IrCl(h2-P,E-PPh2NHP(E)Ph2)]+ (11 and 12). The crystal structure of complex [(h5-C5Me5)RhCl{h2-P,Se-
PPh2NP(Se)Ph2}] has been established by X-ray crystallography. The rhodium atom exhibits a distorted octahedral coordination
with a h5-C5Me5 group occupying the centre of three octahedral sites; a bidentate chelate P,Se-bonded ligand and a chloride atom
complete the metal coordination sphere. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Rhodium; Iridium; Ruthenium; Bis(diphenylphosphine)amine complexes; Monochalcogenide complexes
1. Introduction
In contrast, there are few examples of metal com-
plexes containing monochalcogenide derivatives of the
type Ph2PNHP(E)Ph2. These heterodifunctional li-
gands, containing two types of donor atoms, can show
different coordination modes in their neutral or anionic
form [3b]. Thus, they can act as unidentate P-bonded,
P,E-chelating or bridging ligand with the formation, in
the latter case, of bimetallic complexes [4].
Transition-metal chemistry of bis(diphenylphos-
phine)amine, NH(PPh2)2, has attracted considerable in-
terest in recent years [1], in part due to its chemical and
structural proximity to the widely used diphosphine
CH2(PPh2)2 (dppm). This amine ligand is easily oxi-
dised to form dichalcogenide derivatives NH(EPPh2)2
(E=O, S, Se) which, it turn, can be readily deproto-
nated with alkali metals or metal alcoxides (e.g.
KOBut) to give the corresponding metal salts [2]. The
anions formed, [N(EPPh2)2]−, are versatile ligands able
to form inorganic (carbon-free) chelate rings with a
variety of transition metals [3].
Following our interest in the coordination behaviour
of short-bite bidentate phosphine ligands [1b,3a,4e,5],
we report in this paper the synthesis and characterisa-
tion of new mononuclear neutral complexes of general
formula [(ring)MCl2
(h1-P-PPh NHP(E)Ph )] [(ring)-
2
2
M=(h5-C5Me5)Rh, (h5-C5Me5)Ir, (h6-p-MeC6H4Pri)-
Ru; E=S, Se] and their reactions with chloride sca-
vengers to form neutral or cationic derivatives of the
types [(ring)MCl(h2-P,E-PPh2NP(E)Ph2)] (M=Rh,
Ru) and [(h5-C5Me5)IrCl(h2-P,E-PPh2NHP(E)Ph2)]-
* Corresponding authors. Fax: +34-976-761187.
E-mail address: lahoz@posta.unizar.es (F.J. Lahoz).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01081-6

M. Valderrama et al. / Journal of Organometallic Chemistry 633 (2001) 182–188
183
3
BF4. The crystal structure of [(h5-C5Me5)RhCl{h2-
P,Se-PPh2NP(Se)Ph2}], determined by single-crystal X-
ray diffraction, is also reported.
(6H, d, J(HH)=6.9 Hz, 2 Me(Pri)), 1.88 (3H, s, Me),
2.49 (1H, sp, CH(Pri)), 5.07 (2H, d, AA%, J(HH)=6.0
Hz), 5.33 (2H, dd, BB%, J(HH)=6.0 Hz, J(PH)=1.5
Hz), 5.88 (1H, dd, J(PH)=3.4 Hz, J(PH)=3.0 Hz,
NH). 31P{1H}-NMR (CDCl3, 23 °C): l 50.5 (d,
2J(PAPB)=44.7 Hz, PB), 61.6 (d, PA). IR (KBr, cm−1):
w(P2N) 1100, 848, w(PS) 625, 613.
3
3
2
2
2. Experimental
2.1. General
2.3. Preparation of [(ring)MCl2{p1-P-(Ph2PNH-
P(Se)Ph2}] [(ring)M=(p5-C5Me5)Rh (4), (p5-C5Me5)Ir
(5), (p6-p-MeC6H4Pri)Ru (6)]
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 complexes [{(h5-C5Me5)MCl2}2] (M=Rh, Ir)
[6], [{(h6-p-MeC6H4Pri)RuCl2}2] [7], [(ring)MCl2{h1-P-
The complexes can be prepared by the following two
methods:
(i) A solution of [{(h5-C5Me5)MCl2}2] (0.14 mmol) in
toluene (15 cm3) was treated with the stoichiometric
amount of dppaSe (130 mg, 0.28 mmol). The obtained
solution was stirred at 0 °C for 1 h and then evapo-
rated to dryness. The solid residue was dissolved in the
minimal amount of CHCl3 and the complexes were
precipitated by adding n-hexane.
Ph2PNHPPh2}]
[(ring)M=(h5-C5Me5)Rh,
(h5-
C5Me5)Ir, (h6-p-MeC6H4Pri)Ru] [8] and the ligands
dppa [2c] and dppaE [Ph2PNHP(E)PPh2, E=S, Se]
[4b], were prepared by published procedures. Elemental
analyses (C, H, N, S) were made with a Fisons EA 1108
microanalyser. FTIR spectra were recorded in a Bruker
Vector-22 spectrophotometer using KBr pellets. The
NMR spectra were recorded in Bruker AC-200P or in
Varian Unity 300 spectrometers. Chemical shifts are
reported in ppm relative to SiMe4 (1H) and 85% H3PO4
in D2O (31P, positive shifts downfield) as internal and
external standards, respectively.
4: Yield 207 mg (85%). Anal. Found: C, 52.5; H, 4.7;
N, 1.5. Calc. for C34H36Cl2NP2RhSe: C, 53.8, H, 4.8;
N, 1.8%. 1H-NMR (CDCl3, 23 °C): l 1.37 (d, 15H,
4
C5Me5, J(PAH)=3.8 Hz), 6.29 (s, br, NH). 31P{1H}-
NMR (CDCl3, 23 °C): l 46.1 (d, 2J(PAPB)=46 Hz,
1
1J(PSe)=776 Hz, PB), 67.2 (dd, J(RhPA)=148.3 Hz,
PA). IR (KBr, cm−1): w(P2N) 1099, 930, w(PSe) 552.
5: Yield 163 mg (60%). Anal. Found: C, 47.3; H, 4.1;
N, 1.4. Calc. for C34H36Cl2NP2IrSe: C, 47.3; H, 4.2; N,
1.6%. 1H-NMR (CDCl3, 23 °C): l 1.37 (d, 15H,
2.2. Preparation of [(ring)MCl2{p1-P-Ph2PNH-
P(S)Ph2}] [(ring)M=(p5-C5Me5)Rh (1), (p5-C5Me5)Ir
(2), (p6-p-MeC6H4Pri)Ru (3)]
4
C5Me5, J(PAH)=2.4 Hz), 6.59 (s, br, NH). 31P{1H}-
To
a suspension of the corresponding [(ring)-
2
NMR (CDCl3, 23 °C): l 36.6 (d, J(PAPB)=41.5 Hz,
MCl2{h1-P-(Ph2PNHPPh2}] complex (0.14 mmol) in
Et2O (20 cm3) was added sulphur (0.5 mg, 0.14 mmol).
The suspension was stirred at 0 °C until complete
reaction of the solid sulphur (ca. 3 h). The solution
obtained was evaporated to dryness and the solid
residue extracted with CH2Cl2. Addition of Et2O
caused the precipitation of the complexes.
1
PA), 45.6 (d, J(PSe)=780 Hz, PB). IR (KBr, cm−1):
w(P2N) 1102, 929, w(PSe) 554.
(ii) To
a
suspension of complex [(h6-p-
MeC6H4Pri)RuCl2{h1-P-Ph2PNHPPh2}] (0.14 mmol) in
Et2O (20 cm3) was added grey selenium (11 mg, 0.14
mmol). The mixture was worked up as described for
complexes 1–3.
1: Yield 76 mg (75%). Anal. Found: C, 55.9; H, 4.9;
N, 2.0; S, 4.1. Calc. for C34H36Cl2NP2RhS: C, 56.2, H,
6: Yield 91 mg (82%). Anal. Found: C, 53.4; H, 4.7;
N, 1.8. Calc. for C34H35Cl2NP2RuSe: C, 53.0, H, 4.7;
N, 1.8%. 1H-NMR (CDCl3, 23 °C): l 0.84 (6H, d,
3J(HH)=6.9 Hz, 2Me(Pri)), 1.87 (3H, s, Me), 2.49 (1H,
1
5.0; N, 1.9; S, 4.4%. H-NMR (CDCl3, 23 °C): l 1.37
(15H, C5Me5, 4J(PAH)=3.8 Hz), 6.23 (s, br, NH).
31P{1H}-NMR (CDCl3, 23 °C): l 51.3 (d, J(PAPB)=
2
3
sp, CH(Pri)), 5.07 (2H, d, AA%, J(HH)=6.2 Hz), 5.70
45.4 Hz, PB), 65.4 (dd, 1J(RhPA)=148 Hz, PA). IR
(KBr, cm−1): w(P2N) 1101, 931, w(PS) 623, 613.
2: Yield 75 mg (66%). Anal. Found: C, 50.3; H, 4.3;
N, 1.6, S, 3.6. Calc. for C34H36Cl2NP2IrS: C, 50.1, H,
3
(2H, dd, BB%, J(HH)=6.2 Hz, J(PH)=1.5 Hz), 5.95
(1H, dd, 2J(PH)=2.2 Hz, 2J(PH)=2.2 Hz, NH).
2
31P{1H}-NMR (CDCl3, 23 °C): l 45.3 (d, J(PAPB)=
1
45.7 Hz, J(PSe)=782 Hz, PB), 62.7 (d, PA). IR (KBr,
1
cm−1): w(P2N) 1100, 849, w(PSe) 549.
4.4; N, 1.7; S, 3.9%. H-NMR (CDCl3, 23 °C): l 1.37
4
(d, 15H, C5Me5, J(PAH)=2.4 Hz), 6.54 (s, br, NH).
31P{1H}-NMR (CDCl3, 23 °C): l 35.3 (d, J(PAPB)=
2
2.4. Preparation of [(ring)MCl{p2-P,S-Ph2PN-
P(S)Ph2}] [(ring)M=(p5-C5Me5)Rh (7),
(p6-p-MeC6H4Pri)Ru (8)]
41 Hz, PA), 51.2 (d, PB). IR (KBr, cm−1): w(P2N) 1103,
930, w(PS) 624, 613.
3: Yield 84 mg (80%). Anal. Found: C, 56.2; H, 4.9;
N, 1.9; S, 4.2. Calc. for C34H35Cl2NP2RuS: C, 56.4, H,
4.9; N, 1.9; S, 4.4%. H-NMR (CDCl3, 23 °C): l 0.82
To a solution of [{(ring)MCl2}2] (0.2 mmol) in a
1
mixture of Me2CO–CH2Cl2 (15 cm3, 2:1 v/v) was added

184
M. Valderrama et al. / Journal of Organometallic Chemistry 633 (2001) 182–188
1
dppaS (167 mg, 0.4 mmol) and AgBF4 (79.4 mg, 0.4
mmol). The mixture was stirred for 1 h at room tempe-
rature (r.t.). The AgCl formed was filtered off through
Kieselguhr and the solution was evaporated to dryness.
The residue was dissolved in CH2Cl2, chromatographed
(Kieselgel) and eluted with CH2Cl2. The solution was
concentrated to a small volume and the complexes were
precipitated by adding Et2O.
C34H34ClNP2RuSe: C, 55.6; H, 4.7; N, 1.9%. H-NMR
(CDCl3, 23 °C): l 0.83 (3H, d, 3J(HH)=6.9 Hz,
Me(Pri)), 1.09 (3H, d, J(HH)=6.9 Hz, Me(Pri)), 2.06
3
(3H, s, Me), 2.52 (1H, sp, CH(Pri)), 4.27 (1H, d,
3J(HH)=5.7 Hz), 5.01 (1H, d, J(HH)=6.2 Hz), 5.54
3
3
3
(1H, d, J(HH)=5.7 Hz), 5.77 (1H, d, J(HH)=6.2
Hz). 31P{1H}-NMR (CDCl3, 23 °C):
l 50.6 (d,
1
J(PAPB)=52.4 Hz, J(PSe)=468 Hz, PB), 86.3 (d, PA).
7: Yield 190 mg (69%). Anal. Found: C, 59.3; H, 5.2;
N, 1.9; S, 4.4. Calc. for C34H35ClNP2RhS: C, 59.2; H,
IR (KBr, cm−1): w(P2N) 1102, 839, w(PSe) 546.
1
5.1; N, 2.0; S, 4.7%. H-NMR (CDCl3, 23 °C): l 1.48
2.6. Preparation of [(p5-C5Me5)IrCl(p2-P,E-Ph2PNH-
P(E)Ph2)]BF4. [E=S (11), Se (12)]
(d, 15H, C5Me5, 4J(PAH)=3.0 Hz). 31P{1H}-NMR
2
(CDCl3, 23 °C): l 61.9 (d, J(PAPB)=36 Hz, PB), 79.5
1
(dd, J(RhPA)=127 Hz, PA). IR (KBr, cm−1): w(P2N)
The complexes can be prepared by the following two
methods:
1106, 931, w(PS) 573.
8: Yield 133 mg (51%). Anal. Found: C, 59.1; H, 4.9;
N, 2.0; S, 4.9. Calc. for C34H34ClNP2RuS: C, 59.4; H,
(i) To a solution of complex [{(h5-C5Me5)IrCl2}2]
(100 mg, 0.13 mmol) in a 1:1 mixture of CH2Cl2–
Me2CO (20 cm3) was added dppaE [0.25 mmol; E=S
(105.2 mg), Se (113.5 mg)] and AgBF4 (50 mg, 0.26
mmol). The mixture was stirred for 3 h at r.t. The AgCl
formed was filtered off through Kieselguhr and the
solution was concentrated to a small volume (ca. 2 cm3)
under reduced pressure. The complexes were precipi-
tated by addition of Et2O.
1
5.0; N, 2.0; S, 4.7%. H-NMR (CDCl3, 23 °C): l 0.80
(3H, d, 3J(HH)=6.9 Hz, Me(Pri)), 1.13 (3H, d,
3J(HH)=6.9 Hz, Me(Pri)), 2.10 (3H, s, Me), 2.53 (1H,
3
sp, J(HH)=6.9 Hz, CH(Pri)), 4.20 (1H, d, J(HH)=
3
5.6 Hz), 5.14 (1H, d, J(HH)=6.2 Hz), 5.47 (1H, d,
3J(HH)=5.6 Hz), 5.78 (1H, d, 3J(HH)=6.2 Hz).
31P{1H}-NMR (CDCl3, 23 °C): l 71.1 (d, J(PAPB)=
46.9 Hz, PB), 85.4 (d, PA). IR (KBr, cm−1): w(P2N)
1104, 839, w(PS) 559.
11: Yield 144 mg (66%). 12. Yield 139 mg (61%).
(ii) To a solution of complex [(h5-C5Me5)IrCl2(h1-P-
Ph2PNHP(E)Ph2)] (0.12 mmol) in a 2:1 mixture of
CH2Cl2–Me2CO (15 cm3) was added AgBF4 (25 mg
0.13 mmol). The mixture was stirred for 1 h at r.t. The
AgCl formed was filtered off through Kieselguhr and
the solution evaporated to dryness. The residue was
dissolved in CH2Cl2, chromatographed (neutral alu-
minium oxide, Brockmann I) and eluted with CH2Cl2.
The solution was concentrated to a small volume and
the complexes were precipitated by the addition of Et2O.
11: Yield 76 mg (63%). Anal. Found: C, 46.8; H, 4.2;
N, 1.6; S, 3.6. Calc. for C34H36ClNP2BF4IrS: C, 47.1;
Similar results were obtained reacting complexes 1 or
3 with AgBF4 or AgPF6 in Me2CO solution and work-
ing up as described above.
2.5. Preparation of [(ring)MCl{p2-P,Se-Ph2PN-
P(Se)Ph2}] [(ring)M=(p5-(C5Me5)Rh (9),
(p6-p-MeC6H4Pri)Ru (10)]
To a solution of [{(ring)MCl2}2] (0.2 mmol) in a
mixture of CH2Cl2–Me2CO (15 cm3, 2/1 v/v) was
added dppaSe (186 mg, 0.4 mmol) and AgBF4 (79.4
mg, 0.4 mmol). The mixture was stirred for 1 h at r.t.
The AgCl formed was filtered off through Kieselguhr
and the solution was evaporated to dryness.
1
H, 4.2; N, 1.6; S, 3.7%. H-NMR (CDCl3, 23 °C): l
4
1.57 (d, 15H, C5Me5, J(PAH)=2.4 Hz), 8.68 (s, br,
NH). 31P{1H}-NMR (CDCl3, 23 °C): l 60.9 (d,
J(PAPB)=32.0 Hz, PA), 69.0 (d, PB). IR (KBr, cm−1):
w(P2N) 1108, 941, w(PS) 584.
9: The residue was dissolved in the minimal amount
of Me2CO and the complex was precipitated by adding
n-hexane. Yield 218 mg (74%). Anal. Found: C, 50.9;
H, 4.4; N, 1.7. Calc. for C34H35ClNP2RhSe: C, 51.7; H,
4.5; N, 1.7%. 1H-NMR (CDCl3, 23 °C): l 1.49 (d, 15H,
C5Me5, 4J(PAH)=3.0 Hz). 31P{1H}-NMR (CDCl3,
12: Yield 79 mg (70%). Anal. Found: C, 45.0; H, 3.8;
N, 1.3. Calc. for C34H36ClNP2BF4IrSe: C, 44.7; H, 4.0;
N, 1.5%. 1H-NMR (CDCl3, 23 °C): l 1.60 (d, 15H,
4
C5Me5, J(PAH)=2.5 Hz), 8.72 (s, br, NH). 31P{1H}-
2
1
23 °C): l 40.1 (d, J(PAPB)=41.2, J(PSe)=458 Hz,
PB), 79.7 (dd, 1J(RhPA)=130 Hz, PA). IR (KBr,
cm−1):w(P2N) 1103, w(PSe) 544.
NMR (CDCl3, 23 °C): l 53.6 (d, J(PAPB)=34.0 Hz,
PA), 63.8 (d, PB). IR (KBr, cm−1): w(P2N) 1104, 944,
w(PSe) 549.
10: The residue was dissolved in CH2Cl2, chro-
matographed (neutral aluminium oxide, Brockmann I)
and eluted with CH2Cl2–Me2CO (1:10). The solution
obtained was evaporated to dryness, the residue dis-
solved in the minimal amount of CH2Cl2 and the
complex was precipitated by adding Et2O. Yield 147 mg
(50%). Anal. Found: C, 56.1; H, 4.7; N, 1.9. Calc. for
2.7. Crystal structure of complex [(p5-C5Me5)RhCl{p2-
P,Se-Ph2PNP(Se)Ph2}]·CH2Cl2 (9)
A summary of crystal data, and refinement parame-
ters for the structural analysis is reported in Table 1.
Suitable crystals were obtained from a slow diffusion of

M. Valderrama et al. / Journal of Organometallic Chemistry 633 (2001) 182–188
185
3. Results and discussion
Et2O into CH2Cl2 solution of complex 9; a yellow
irregular block (0.25×0.18×0.15 mm) was mounted
on a four-circle diffractometer (Siemens P4) working
with graphite-monochromated Mo–Ka radiation (u=
The dinuclear complexes [{(ring)MCl2}2] ((ring)M=
(h5-C5Me5)Rh, (h5-C5Me5)Ir and (h6-p-MeC6H4Pri)-
Ru) reacted with bis(diphenylphosphino)-amine [NH-
(PPh2)2, dppa] in toluene by cleavage of the chlorine
bridges to yield neutral complexes with the dppa acting
as a monodentate P-donor ligand [8].
,
0.71073 A) and operating at 200 K. Precise lattice
parameters were determined by least-squares fit from
94 centred reflections in the region 2552q538°.
Three standard reflections were monitored every 97
measured reflections to check crystal and instrument
stability throughout data collection; a 2.46% decay of
the intensities was observed. All data were corrected
for Lorentz and polarisation effects, and a semiempiri-
cal („-scan method) absorption correction was also
applied [9a]. The structure was solved by Patterson and
conventional Fourier techniques, and refined by full-
1/2[{(ring)})MCl2}2]+NH(PPh2)2
“[(ring)MCl2(h1-P-Ph2PNHPPh2)]
(1)
When the ligand dppa acts as a unidentate P-donor
ligand, the second uncoordinate P atom has proved to
remain reactive. Thus, the mononuclear complexes re-
acted with elemental sulphur or selenium in diethyl
ether creating the P-coordinate monosulphide or
monoselenide ligands and leading to complexes of the
type [(ring)MCl2{h1-P-Ph2PNHP(S)Ph2}] ((ring)M=
(h5-C5Me5)Rh (1), (h5-C5Me5)Ir (2), (h6-p-MeC6-
H4Pri)Ru (3)) and [(ring)MCl2{h1-P-Ph2PNHP(Se)-
Ph2}] ((ring)M=(h5-C5Me5)Rh (4), (h5-C5Me5)Ir (5),
(h6-p-MeC6H4Pri)Ru (6)). Alternatively, complexes 1–
6 can be prepared by reaction of the dimeric complexes
[{(ring)MCl2}2] with the stoichiometric amounts of the
ligands Ph2PNHP(S)Ph2 and PPh2NHP(Se)Ph2, pre-
viously synthesised.
matrix least-squares methods on F2
(SHELXL-97) [9b]
with initial isotropic thermal parameters. Anisotropic
thermal parameters were used in the last cycles of
refinement for all non-hydrogen atoms. Hydrogen
atoms for methyl groups were included in calculated
,
positions (CꢀH=0.98 A), and the remaining hydro-
gens were located in difference Fourier maps; all were
included in the refinement riding on their respective
carbon atom with two different common isotropical
thermal parameters.
Interestingly, treatment of these complexes with
AgBF4 or AgPF6 in a 1:1 molar ratio affords two
different types of complexes. When the reaction was
carried out starting from Rh(1, 4) or Ru (3, 6) deriva-
tives, neutral complexes of general formula
[(ring)MCl{h2-P,E-Ph2PNP(E)Ph2}] (E=S; (ring)M=
(h5-C5Me5)Rh (7), (h6-p-MeC6H4Pri)Ru (8); E=Se;
(ring)M=(h5-C5Me5)Rh (9), (h6-p-MeC6H4Pri)Ru
(10)) were obtained. In these reactions, the easy loss of
the amine proton is caused by the increase of its acidity
produced by the coordination of the free PE group to
the metal centre. Similar results were obtained treating
the starting dimeric complexes [{(ring)MCl2}2] with the
monochalcogenide ligands Ph2PNHP(S)Ph2 (dppaS)
and Ph2PNHP(Se)Ph2 (dppaSe) in the presence of sil-
ver salts. However, reactions performed with the iri-
dium complexes (2, 5) yield the cationic compounds
[(h5-C5Me5)IrCl(h2-P,E-Ph2PNHP(E)Ph2)]BF4 [E=S
(11), Se (12)]. These results confirm that the iridium
centre is softer than the corresponding Rh or Ru cen-
tres and, in this case, the acidity of the amine proton is
not en-hanced enough by the h2-coordination of the
ligand. All these reactions are summarised in Scheme
1.
Table 1
Crystallographic data and structure refinement parameters for com-
plex 9
Empirical formula
Formula weight
Crystal system
Space group
Unit cell dimensions
C34H35ClNP2RhSe·CH2Cl2
821.82
Triclinic
(
P1
,
a (A)
8.6592(6)
11.1095(8)
19.0300(14)
86.928(5)
82.696(5)
70.593(5)
1712.5(3)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
Dcalc (Mg m−3
)
1.594
1.915
v (mm−1
)
q Range for data collection (°)
Index ranges
2.16–27.50
−15h511, −135k514,
−245l524
9713
7823 (Rint=0.0352)
7823/0/395
1.000
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
a
R1 [I\2|(I)]
0.0455
0.0828
b
wR2 (all data)
Largest difference peak and hole 0.579 and −0.527
All complexes were isolated as stable microcrys-
talline solids. Their solid-state IR spectra in KBr pel-
lets showed the characteristic absorptions of the P2N
moiety, together with the absorption of the uncoordi-
nated or coordinated PꢁE groups. The P2N fragment
−3
,
(e A
)
a R1=ꢀꢁFoꢂ−ꢂFcꢁ/ꢀꢂFoꢂ for 5155 reflections.
b wR2=[ꢀ[w(F2o−Fc2)2]/ꢀ[w(F2o)2]]1/2; w−1=[|2(F2o)+(0.0275P)2+
0.4909P], where P=[max(F2o, 0)+2Fc2)]/3.

186
M. Valderrama et al. / Journal of Organometallic Chemistry 633 (2001) 182–188
Scheme 1.
Table 2
31P{1H}-NMR chemical shifts (l ppm) and coupling constants (Hz) of the isolated complexes a
b
Complex
PA
PB
2J(PAPB)
(1) [(h5-C5Me5)RhCl2{h1-P-Ph2PNHP(S)Ph2}] c
(2) [(h5-C5Me5)IrCl2{h1-P-Ph2PNHP(S)Ph2}]
65.4 (dd)
35.3 (d)
61.6 (d)
67.2 (dd)
36.6 (d)
62.7 (d)
79.5 (dd)
85.4 (d)
79.7 (dd)
86.3 (d)
60.9 (d)
53.6 (d)
51.3 (d)
51.2 (d)
50.5 (d)
46.1 (d)
45.6 (d)
45.3 (d)
61.9 (d)
71.1 (d)
40.1 (d)
50.6 (d)
69.0 (d)
63.8 (d)
45.4
41.0
44.7
46.0
41.5
45.7
36.0
46.9
41.2
52.4
32.0
34.0
(3) [(h6-p-MeC6H4Pri)RuCl2{h1-P-Ph2PNHP(S)Ph2}]
(4) [(h5-C5Me5)RhCl2{h1-P-Ph2PNHP(Se)Ph2}] d
(5) [(h5-C5Me5)IrCl2{h1-P-Ph2PNHP(Se)Ph2}] e
(6) [(h6-p-MeC6H4Pri)RuCl2{h1-P-Ph2PNHP(Se)Ph2}] f
(7) [(h5-C5Me5)RhCl{h2-P,S-Ph2PNP(S)Ph2}] g
(8) [(h6-p-MeC6H4Pri)RuCl{h2-P,S-Ph2PNP(S)Ph2}]
(9) [(h5-C5Me5)RhCl{h2-P,Se-Ph2PNP(Se)Ph2}] h
(10) [(h6-p-MeC6H4Pri)RuCl{h2-P,Se-Ph2PNP(Se)Ph2}] i
(11) [(h5-C5Me5)IrCl{h2-P,S-Ph2PNHP(S)Ph2}]BF4
(12) [(h5-C5Me5)IrCl{h2-P,Se-Ph2PNHP(Se)Ph2}]BF4
a Measured in CDCl3 at room temperature. Chemical shifts relative to H3PO4 (85%) in D2O as external standard.
b 31P-NMR of free ligands {(CD3)2SO}: dppaS, l 27.6 (d, 2J(PP)=86 Hz, P) and 60.9 (d, PS); dppaSe, l 29.3 (d, 2J(PP)=93 Hz, P) and 58.2
(d, 1J(PSe)=757 Hz, PSe) [4b].
c 1J(RhP)=148 Hz.
d 1J(RhP)=148.3 Hz, 1J(PSe)=776 Hz.
e 1J(PSe)=780 Hz.
f 1J(PSe)=782 Hz.
g 1J(RhP)=127 Hz.
h 1J(RhP)=130 Hz, 1J(PSe)=458 Hz.
i 1J(PSe)=468 Hz.
shows two bands in the ranges 1099–1108 and 839–940
cm−1, reflecting the increase of the PꢀN bond order
compared with the free ligands [dppaS, wasym(P2N)=
791 and wsym(P2N)=696 cm−1; dppaSe, wasym(P2N)=
790 and wsym(P2N)=686 cm−1] [4b]. As expected, the
w(PS) stretching in complexes 7, 8, and 11 [w(PS)=
584–559 cm−1] were shifted to lower frequencies rela-
tive to those observed in complexes 1–3
However, the w(PSe) absorption in complexes 9, 10, and
12 [w(PSe)=546–549 cm−1], showed no significant
variations with respect to complexes 4–6 [w(PSe)=
552–554 cm−1] or to the free ligand [w(PSe)=551
cm−1] [4b].
The 31P{1H}-NMR data for the complexes 1–12 are
given in Table 2. Couplings with the 77Se and 103Rh
nuclei help us in the spectral assignments. As a conse-
quence of the coordination, a large deshielding was
observed for the PA phosphorus nucleus with respect to
the free ligand. The smaller shifts for the iridium com-
[w(PS)=613–625 cm−1
] and in the free ligands
[w(PS)=634 cm−1] [4b], most likely as a consequence
of the decrease of the bond order upon coordination.

M. Valderrama et al. / Journal of Organometallic Chemistry 633 (2001) 182–188
187
Table 3
plexes 2 and 5 are consistent with the usual for ligands
,
Selected bond lengths (A) and bond angles (°) for complex 9
attached to heavier transition metals [10]. The PB atom
of complexes 7 and 8 shows a large deshielding upon
coordination of the sulphur atom to the metal centre.
This shift is probably due to the chelate ring stabilising
Bond lengths
RhꢀCl
RhꢀSe
RhꢀP(1)
RhꢀC(25)
RhꢀC(26)
RhꢀC(27)
RhꢀC(28)
RhꢀC(29)
2.3991(12)
2.5067(6)
2.3195(11)
2.224(4)
2.171(4)
2.206(4)
2.195(4)
2.230(4)
SeꢀP(2)
P(1)ꢀN
P(1)ꢀC(1)
P(1)ꢀC(7)
P(2)ꢀN
P(2)ꢀC(13)
P(2)ꢀC(19)
2.1940(12)
1.642(3)
1.826(4)
1.838(4)
1.582(3)
1.809(4)
1.820(4)
1
effect [11]. Interestingly, the J(PSe) coupling decreases
ca. 300 Hz when the selenium coordinates to the metal.
This reduction could be related to a decreasing of the
PꢁSe double bond character upon coordination [4d].
1
The H-NMR spectra of complexes 1–12 exhibited
the expected resonances corresponding to the coordi-
nated C5Me5 and p-MeC6H4Pri groups. Moreover,
complexes 11 and 12 show a broad singlet at l 8.68 and
8.72 ppm, respectively, assigned to the amine proton.
Bond angles
ClꢀRhꢀSe
91.09(3)
87.23(4)
122.98(16)
88.18(3)
121.36(14)
133.80(14)
98.86(3)
121.0(2)
115.89(13)
115.15(14)
RhꢀP(1)ꢀC(7)
NꢀP(1)ꢀC(1)
NꢀP(1)ꢀC(7)
C(1)ꢀP(1)ꢀC(7)
SeꢀP(2)ꢀN
SeꢀP(2)ꢀC(13)
SeꢀP(2)ꢀC(19)
NꢀP(2)ꢀC(13)
NꢀP(2)ꢀC(19)
C(13)ꢀP(2)ꢀC(19)
114.58(14)
104.33(12)
102.92(19)
102.21(19)
113.46(13)
112.52(15)
107.02(14)
109.8(2)
ClꢀRhꢀP(1)
ClꢀRhꢀG*
SeꢀRhꢀP(1)
SeꢀRhꢀG*
P(1)ꢀRhꢀG*
RhꢀSeꢀP(2)
P(1)ꢀNꢀP(2)
RhꢀP(1)ꢀN
RhꢀP(1)ꢀC(1)
3.1. Molecular structure of [(p5-C5Me5)-
RhCl{p2-P,Se-Ph2PNP(Se)Ph2}]·CH2Cl2 (9)
110.85(19)
102.67(19)
A view of the neutral complex 9, including the atom
numbering scheme, is shown in Fig. 1. The most rele-
vant bond distances and angles are collected in Table 3.
In these complexes, the rhodium atom exhibits a dis-
torted octahedral coordination sphere with the pen-
tamethylcyclopentadienyl ligand formally occupying
three octahedral sites; a heterodifunctional chelate li-
gand bonded to the metal centre through a phosphorus
and a selenium atom, and a chloride atom complete the
coordination sphere. This particular coordination
makes each rhodium centre chiral, although, obviously,
both enantiomers are present in the crystal structure.
The methyl substituents are bent away from the
rhodium atom and the RhꢀG (C5Me5 centroid) distance
*G represents the centroid of the h5-C5Me5 ligand.
symmetrical complex [(h5-C5Me5)RhCl{h2-Se,Se%-
(SePPh2)2N}] [RhꢀCl: 2.4365(18), RhꢀSe: average
,
,
2.563(1)A] [3a]. The RhꢀCl and RhꢀP(1) [2.3195(11) A]
distances agree well with the values found in the related
complex
[(h5-C5Me5)RhCl{prophos}]BF4
[RhꢀCl:
,
,
2.393(1)A, RhꢀP: 2.325(1) A] [14].
The bidentate chelate ligand forms an approximately
planar pentaatomic metallacycle. The bonding parame-
,
ters within the RhP2NSe ring [P(2)ꢀSe: 2.1940(12) A,
,
,
P(2)ꢀN: 1.582(3)A, P(1)ꢀN: 1.642(3)
A
and
,
is 1.839(5) A [individual RhꢀC bond distances range
P(1)ꢀNꢀP(2): 121.0(2)°] indicate some grade of p-delo-
,
from 2.171(5) to 2.231(4) A] and compares well with the
calisation over the fragment SeꢀPꢀNꢀP (PꢀSe in neutral
values reported for related pentamethylcyclopentadi-
,
ligand NH(SePPh2)2: 2.100(3) A [15]; single covalent
enyl rhodium(III) compounds [(h5-C5Me5)Rh{h3-
,
bond PꢀN: 1.78 A [16]). Similar PꢀNꢀP bond se-
,
Se,Se%,C-(SePPh2)2CH}]ClO4 [1.807(10) A] [12] and
quences, with comparable bond lengths are commonly
found in tri- or tetracyclophosphacenes [17]. These
bonding parameters are similar to those in cis-[Pt{h2-
5
2
1
,
[(h -C5Me5)Rh(h -S2PPh2)(h -SPPh2)] [1.852(3) A] [13].
,
,
The RhꢀCl [2.3991(12) A] and RhꢀSe [2.5067(6) A]
distances are slightly shorter than those reported for the
,
P,Se-Ph2P(Se)NPPh2}2] [PꢀSe: 2.200(2) A, P(2)ꢀN:
,
,
A and P(1)ꢀNꢀP(2):
1.584(7)A, P(1)ꢀN: 1.635(6)
123.3(4)°] [2b] and trans-[ReO(OEt){Ph2P(Se)NPPh2}2]
,
,
[PꢀSe: 2.208(3) A, P(2)ꢀN: 1.579(8)A, P(1)ꢀN: 1.639(8)
,
A and P(1)ꢀNꢀP(2): 122.0(5)°] [18].
4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 154780 for compound 9.
Copies of the information may be obtained free of
charge from the Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
ccdc.ca.ac.uk).
Fig. 1. Molecular representation of the neutral complex 9 with the
labelling scheme used (H atoms omitted for clarity).

188
M. Valderrama et al. / Journal of Organometallic Chemistry 633 (2001) 182–188
(e) D.J. Williams, A.M.Z. Slawin, J.R. Phillips, J.D. Woollins,
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