Synthesis, characterization, and reactivity of cationic palladium(II) and platinum(II) iodo complexes containing a linear or a tripodal aminophosphine the. X-ray crystal structures of [Pd{HN(CH2CH2PPh2)2}I]I and [Pd3{N(CH2CH2PPh2}3) 2I4]I2

Article abstract of DOI:10.1002/1521-3749(200206)628:5<1075::AID-ZAAC1075>3.0.CO;2-M

The complexes [M(PNHP)I]I (PNHP = bis[2-(diphenylphosphino)ethyl]amine; M = Pd (1), Pt (2)) and [M(NP₃)I]I (NP₃ = tris[2-(diphenylphosphino)ethyl]amine; M = Pd (3), Pt (4)) were prepared by interaction of the appropriate aminophosphine in CH₂Cl₂ with aqueous solutions containing [MCl₄]^2- salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt₂(PNHP)₃]I₄ (2a) and [Pd₃(NP₃)₂I₄]I₂ (3a) in the presence of coordinating solvents such as the mixture CD₃OD/D₂O/DMSO-d₆ and CH₂Cl₂/CH₃OH, respectively. Complex 1 consists of distorted square-planar cations [Pd(PNHP)I]⁺ and iodide anions able to establish short N-H···I interactions of 2.850 A. The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square-planar Pd^II atoms, PdNP₂I and trans-PdP₂I₂, NP₃ acting as tridentate chelating and bridging ligand, respectively. On the basis of ³¹P {¹H} NMR data it has been shown that each distorted square-planar Pt(II) centre of 2a contains one PNHP acting as tridentate chelating ligand with the other aminophosphine bridging the two metals via the P atoms. Complexes 3 and 4 were shown by ³¹P {¹H} NMR to have the metal atom bound to the three P atoms of NP₃ and one iodo ligand. Additions of AcCysSH and GSH to 4 result, by a ring-opening process, in the formation of [Pt(NP₂PO)(SR)] (RS = Acys (4a), GS (4b)) in which the ligand contains a dangling arm phosphine oxide group and the platinum atom achieves the four-coordination involving the N atom of the aminophosphine. Compounds [Pt₂(PNHP)₃]Cl₄ (2a′, 2a″), [PtAu(PNHP)₂I]I₂ (2b), and [Pt(PNHP)(ONO₂)](NO₃) (2c) were detected in some extent in solution by reaction of complex 2 with Au(tdg)Cl (tdg = thiodiglycol), AuI and excess AgNO₃, respectively. While 1 does not react with AuI, complex 3 affords the heterobimetallic complexes PdCu(NP₃)I₃ (5), PdAg₂(NP₃)I₄ (6) and PdAu(NP₃)I₃ (7) by interaction with the appropriate iodide M′I (M′ = Cu, Ag, Au) via a chelate ring-opening.

Full text of DOI:10.1002/1521-3749(200206)628:5<1075::AID-ZAAC1075>3.0.CO;2-M

Synthesis, Characterization, and Reactivity of Cationic Palladium(II) and
Platinum(II) Iodo Complexes Containing a Linear or a Tripodal
Aminophosphine.
The X-Ray Crystal Structures of [Pd{HN(CH2CH2PPh2)2}I]I and
[Pd3{N(CH2CH2PPh2}3)2I4]I2
a
b
a
b
´
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´
M. Ines Garcıa-Seijo , Abraha Habtemariam , Damian Fernandez-Anca , Simon Parsons , and
a,*
´
´
M. Esther Garcıa-Fernandez
a
Santiago de Compostela/Spain, Department of Inorganic Chemistry, University of Santiago de Compostela
b
Edinburgh/U.K., Department of Chemistry, University of Edinburgh, King’s Buildings
Received December 17th, 2001.
Dedicated to Professor Joachim Strähle on the Occasion of his 65th Birthday
Abstract. The complexes [M(PNHP)I]I (PNHP ϭ bis[2-(diphenyl-
phosphino)ethyl]amine; M ϭ Pd (1), Pt (2)) and [M(NP3)I]I
(NP3 ϭ tris[2-(diphenylphosphino)ethyl]amine; M ϭ Pd (3), Pt (4))
were prepared by interaction of the appropriate aminophosphine
in CH2Cl2 with aqueous solutions containing [MCl4]2Ϫ salts and
NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear com-
pounds [Pt2(PNHP)3]I4 (2a) and [Pd3(NP3)2I4]I2 (3a) in the pres-
ence of coordinating solvents such as the mixture CD3OD/D2O/
DMSO-d6 and CH2Cl2/CH3OH, respectively. Complex 1 consists
of distorted square-planar cations [Pd(PNHP)I]ϩ and iodide
dentate chelating ligand with the other aminophosphine bridging
the two metals via the P atoms. Complexes 3 and 4 were shown by
31P {1H} NMR to have the metal atom bound to the three P atoms
of NP3 and one iodo ligand. Additions of AcCysSH and GSH to
4
result, by a ring-opening process, in the formation of
[Pt(NP2PO)(SR)] (RS ϭ Acys (4a), GS (4b)) in which the ligand
contains a dangling arm phosphine oxide group and the platinum
atom achieves the four-coordination involving the N atom of the
aminophosphine. Compounds [Pt2(PNHP)3]Cl4 (2aЈ, 2aЉ),
[PtAu(PNHP)2I]I2 (2b), and [Pt(PNHP)(ONO2)](NO3) (2c) were
detected in some extent in solution by reaction of complex 2 with
Au(tdg)Cl (tdg ϭ thiodiglycol), AuI and excess AgNO3, respec-
tively. While 1 does not react with AuI, complex 3 affords the het-
erobimetallic complexes PdCu(NP3)I3 (5), PdAg2(NP3)I4 (6) and
PdAu(NP3)I3 (7) by interaction with the appropriate iodide MЈI
(MЈ ϭ Cu, Ag, Au) via a chelate ring-opening.
˚
anions able to establish short N-H···I interactions of 2.850 A. The
aminophosphine adopts a boat conformation and is coordinated
to palladium in a tridentate chelating fashion. The crystal structure
for cations of 3a reveals the presence of two types of distorted
square-planar PdII atoms, PdNP2I and trans-PdP2I2, NP3 acting as
tridentate chelating and bridging ligand, respectively. On the basis
of 31P {1H} NMR data it has been shown that each distorted
square-planar Pt(II) centre of 2a contains one PNHP acting as tri-
Keywords: Palladium; Platinum; Iodo complexes; NMR spec-
troscopy; Polynuclear cationic species; Crystal structures
Synthese, Charakterisierung und Reaktivität der Palladium(II)- und Platin(II)-Iod-
Komplexe mit einem linearen bzw. einem tripodalen Aminophosphan-Liganden. Die
Kristallstrukturen von [Pd{HN(CH2CH2PPh2)2}I]I und [Pd3{N(CH2CH2PPh2)3}2I4]I2
Inhaltsübersicht. Die Komplexe [M(PNHP)I]I (PNHP ϭ Bis[2-(di-
phenylphosphino)ethyl]amin; M ϭ Pd (1), Pt (2)) und [M(NP3)I]I
(NP3 ϭ Tris[2-(diphenylphosphino)ethyl]amin; M ϭ Pd (3), Pt (4))
wurden präpariert durch Umsetzung des betreffenden Aminophos-
phans in CH2Cl2 mit wäßrigen Lösungen der [MCl4]2Ϫ-Salze und
NaI im Verhältnis 1:4. Die Komplexe 2 und 3 bilden die mehrker-
nige Verbindungen [Pt2(PNHP)3]I4 (2a) und [Pd3(NP3)2I4]I2 (3a) in
Gegenwart von Lösungsmittelgemischen wie CD3OD/D2O/
DMSO-d6 bzw. CH2Cl2/CH3OH. Komplex 1 enthält die verzerrt
quadratisch-planaren Kationen [Pd(PNHP)I]ϩ und Iod-Anionen
ten PtII-Atome von 2a ein PNHP als dreizähnigen Chelatliganden
enthält und mit dem anderen Aminophosphan werden die zwei
Metallatome verbrückt. In den Komplexen 3 und 4 ist nach den
31P{1H}-NMR-Daten das Metallatom an die drei P-Atome des
NP3 und an einen Iod-Liganden gebunden.
Zusatz der Thiole AcCysSH und GSH zu 4 führt zu einer
Ringöffnung und Bildung von [Pt(NP2PO)(SR)] (RS ϭ Acys (4a),
GS (4b)) in denen der Ligand eine angehängte Phosphanoxid-
Gruppe enthält und das Platinatom vierfache Koordination erre-
icht unter Einbeziehung des N-Atoms des Aminophosphans. Die
Verbindungen [Pt2(PNHP)3]Cl4 (2aЈ, 2aЉ), [PtAu(PNHP)2I]I2 (2b)
und [Pt(PNHP)(ONO2)](NO3) (2c) wurden in Lösung bei der Re-
aktion von 2 mit Au(tdg)Cl (tdg ϭ Thiodiglykol), AuI bzw. einem
ξberschuß an AgNO3 beobachtet. Während 1 nicht mit AuI reagirt,
ergibt 3 die heterobimetallischen Komplexe PdCu(NP3)I3 (5),
PdAg2(NP3)I4 (6) und PdAu(NP3)I3 (7) beim Umsatz mit den Iod-
iden von Cu, Ag bzw. Au durch die Ringöffnungsreaktion.
˚
mit kurzen NϪH···I-Kontakten von 2,850 A. Aminophosphan hat
Boot-Konformation und ist dreizähnig, chelatartig an Palladium
koordiniert. Die Kristallstruktur der Kationen von 3a zeigt die
Anwesenheit von zwei Arten von verzerrt quadratisch-planaren
PdII-Atomen in PdNP2I und trans-PdP2I2; NP3 ist ein dreizähniger
Chelat- bzw. ϪBrückenligand. Auf Basis der 31P{1H}-NMR-Daten
wird gezeigt, dass jedes der verzerrt quadratisch-planar koordinier-
Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044Ϫ2313/02/628/1075Ϫ1084 $ 20.00ϩ.50/0
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M. I. Garcıa-Seijo, A. Habtemariam, D. Fernandez-Anca, S. Parsons, M. E. Garcıa-Fernandez
Introduction
The flexible coordination behaviour of hemilabile ligands
containing “soft” and “hard” donor atoms such as phos-
phorus and nitrogen, respectively, have been exploited to
maximize the stability of a series of metal complexes impli-
cated in several catalytic and biologically relevant reactions
[1Ϫ3]. The coordination chemistry of terdentate PNP amin-
ophosphines toward palladium(II) has been explored and
PP-dimeric, PNP-monomeric and PP-monomeric modes of
coordination were found [2,4]. Due to the weaker donor
ability of the nitrogen atom to latter transition metal atoms
than phosphines, these complexes can isomerize between cis
and trans configurations the ligand altering between the bi-
and terdentate modes. By changing the steric and electronic
requirements of the R substituent at the nitrogen atom, the
ligand backbone and the other coligands, it is possible to
control metal-nitrogen bond dissociation or association and
consequently improve the catalytic or biological efficiency
of conventional reactions [2,3,5a]. There was no influence
of the coligand in the structures found for PdII and PtII
complexes of the types M(PNP)X [PNP ϭ deprotonated
Z,Z-PPh2CH2CButϭN-NϭCButCH2PPh2, (M ϭ Pd; X ϭ
Cl, Br, Me), (M ϭ Pt; X ϭ Cl, Br, I)] where PNP is acting
as a tridentate chelating ligand [5b] or Pt(PNP)X2 (PNP ϭ
(Cy2PCH2)2NMe, Cy ϭ Cyclohexyl, X ϭ Cl, I) with PNP
adopting a bidentate PP-coordination mode [5c]. However,
while the PtII chloro complex of the ligand, ( R )-N,N-bis(2-
(diphenylphosphino)ethyl)-1-phenyl-ethylamine shows a cis
configuration in cis-Pt(η2-P,P-PNP)Cl2, its reaction with KI
in the presence of SnCl2 leads to the formation of the ionic
complex [Pt(PNP)I](SnCl3) with the nitrogen atom involved
in the coordination to the platinum atom [5a].
Scheme 1 The formation of the diplatinum ionic complex 2a from
solutions of [Pt(PNHP)I]I in CD3OD/D2O/DMSO-d6. Reactions
of [Pt(PNHP)I]I with thiols, gold(I) salts and silver(I) nitrate to
form 2a, (2aЈ, 2aЉ, 2b) and 2c, respectively.
ophosphine arrangement and the iodo ligand substitutions.
We describe the formation of polynuclear cationic com-
plexes, thiolate adducts containing an uncoordinated phos-
phine oxide group and heterobimetallic complexes involving
gold group metal ions which induce a chelate ring-opening
of the precursor.
There are only a few X-ray crystal structures reported in
the literature corresponding to palladium(II) and plati-
num(II) complexes of the aminophosphine bis[2-(diphenyl-
phosphino)ethyl]amine (PNHP) [4,6] and its NH substi-
tuted derivative, tris[2-(diphenylphosphino)ethyl]amine
(NP3) [7Ϫ9]. On the other hand, the structural studies in
solution for halo complexes are very limited [10]. To the
best of our knowledge there are no crystallographic studies
on polynuclear complexes of d8 metal ions with these amin-
ophosphines.
Results and Discussion
Preparations and characterization
The aim of this work is to increase the knowledge on the
coordination chemistry of PNHP and NP3 to latter tran-
sition metals. For this reason we report the preparation and
characterization of the mononuclear iodo compounds
[M(PNHP)I]I and [M(NP3)I]I (M ϭ Pd, Pt) and their reac-
tivity as a function of the metal, the tripodal or linear amin-
Schemes 1 and 2 show the complexes prepared in this work
with the linear aminophosphine PNHP and the tripodal
NP3. Both aminophosphines were synthesized following a
variation of the methods described in the literature [11Ϫ13].
Complexes 1Ϫ4 were obtained from the organic phase by
addition of dichloromethane solutions of the hydrochloride
salt of PNHP or the free NP3 to aqueous solutions of
[MCl4]2Ϫ salts (M ϭ Pd, Pt) in the presence of sodium iod-
ide (M:I ratio 1:4).
The presence of coordinating solvents in solutions of 2
(CD3OD/D2O/DMSO-d6) and 3 (CH2Cl2/CH3OH) allowed
the formation of the dinuclear and trinuclear ionic com-
plexes [Pt2(PNHP)3]I4 (2a) and [Pd3(NP3)2I4]I2 (3a), respec-
tively, complex 2a coexisting with 2. The reactions of solu-
a
´
´
*Dr. M Esther Garcıa Fernandez
Department of Inorganic Chemistry
University of Santiago de Compostela
E-15782 Santiago de Compostela/Spain
Tel: ϩ34(9)81 591076; Fax: ϩ34(9)81 597525
E-mail: qiegfq@usc.es
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Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084

Cationic Palladium(II) and Platinum(II) Iodo Complexes
Complexes 1, 3 Ϫ 6 gave satisfactory microanalyses for
hydrates, while 2 and 7 were isolated as ether and dichloro-
methane solvates, respectively.
The molar conductivities for complexes 1 Ϫ 3 in CH3CN
and for 4 in DMF are indicative of a 1:1 electrolyte behav-
iour. Complexes 5 and 6 behaves as neutral species in 10Ϫ3
M DMF solutions while solutions of 7 in CH3CN are con-
ductors [16].
The FAB mass spectra for complexes 1 Ϫ 4 showed peaks
due to MLI fragments resulting by the loss of the iodo
counteranion. The same tendency of fragmentation was
found for the analogous chloro and bromo complexes
[Pd(PNHP)X]X or [M(triphos)X]X (triphos ϭ bis[2-(di-
phenylphosphino)ethyl]phenylphosphine) [15,17]. Com-
plexes 5 and 7 showed peaks assigned to the fragments
PdMЈ(NP3)I2 (MЈ ϭ Cu, Au) in accordance with the forma-
tion of heterobimetallic compounds.
The N-H vibration observed in the near infrared spectra
(4000 Ϫ 500 cmϪ1) of complexes 1 and 2 is shifted to higher
energy compared to the free amine as a result of the com-
plexation [18]. The far infrared spectra (500Ϫ100 cmϪ1) for
complexes 1Ϫ5 and 7 showed Pd-I stretchs assignable to
terminal bonds [19].
Scheme 2 The formation of the trinuclear ionic complex 3a from
solutions of [Pd(NP3)I]I (3) in CH2Cl2/CH3OH. Reations of 3 with
gold group metal iodides to form 5, 6 and 7 and reactivity of
[Pt(NP3)I]I (4) with thiols to form 4a and 4b.
Structural Studies in Solution: 31P {1H} NMR
Spectra of Complexes 1Ϫ4
The singlets at δ 37.9 for 1 and δ 3.5 and 36.0 (integration
ratio 1:2) for 3 in their 31P {1H} NMR spectra (Table 1) are
indicative of a distorted square-planar geometry at pal-
ladium with PNHP and NP3 acting as PNP and PPP-tri-
dentate chelating ligands, respectively. This contrasts with
the behaviour of the chloro complex [Pd(NP3)Cl]Cl which
seems to involve the N atom of NP3 in the coordination to
the metal [10b,20]. The 31P {1H} NMR spectra for 2 (Fig-
ure 1a) and 4 (Table 1) in CDCl3 and DMSO-d6 consist of
one and two signals, respectively at δ 33.2 and δ -4.4 and
tions of 2 with Au(tdg)Cl in CD2Cl2/CH3OH leads to the
formation of dinuclear ionic species [Pt2(PNHP)3]Cl4 (2aЈ,
2aЉ). Complex 2aЈ was obtained as a solid by reaction of
aqueous solutions of K2[PtCl4] with (PNHP).HCl in di-
chloromethane using the appropriate Pt:(PNHP).HCl ratio,
2:3. When this reaction was carried out using a 1:1 ratio the
diplatinum compound [Pt2(PNHP)3]Cl4 (2aЈ) was majority
revealing that complex [Pt(PNHP)Cl]Cl can not be achieved
under the same experimental conditions as [Pt(PNHP)I]I
(2). Furthermore, the analogous bromo complex was pre-
viously prepared by us [14] as the dinuclear system
[Pt2(PNHP)3]Br4. The formation of [PtAu(PNHP)2I]I2 (2b)
in a mixture with 2 and [Pt(PNHP)(ONO2)](NO3) (2c) in
a mixture with [Pt2(PNHP)3](NO3)2 (2a*) was detected by
reaction of 2 with AuI (CDCl3/CD2Cl2) and excess AgNO3
(CD3OD/D2O/DMSO-d6), respectively.
1
27.6 with J(195Pt,31P) values in accordance with P trans to
P [2625 Hz (2), 2597 Hz (4)] and P trans to I [3726 Hz (4)].
These data suggest for 2 and 4 a square-planar arrangement
to the metal in solution similar to 1 and 3, respectively al-
though on the basis of the broadening of the signals in 4,
the participation in some extent of the N atom in the coor-
dination to platinum should not be excluded.
The reactions of 4 with the thiols AcCysSH and GSH in
DMSO-d6/D2O afford the systems [Pt(NP2PO)(SR)] [RS ϭ
ACysS (4a), GS (4b)]. By addition of an small excess of CuI
and AuI over the 1:1 stoichiometric ratio to dichlorometh-
ane solutions of 3, complexes PdCu(NP3)I3 (5) and
PdAu(NP3)I3 (7) were obtained, respectively. The formation
of a heterobimetallic PdAg complex required the use of a
1:2 stoichiometric ratio in PdAg2(NP3)I4 (6). Attempts to
obtain heterobimetallic complexes of the types
PdMЈ(PNHP)I3 and PtMЈ(PNHP)I3 (MЈ ϭ Cu, Ag, Au)
starting from 1 and 2 were unsuccessful as was previously
observed for [Pd(PNHP)X]X (X ϭ Cl, Br) [15].
The 31P {1H} NMR spectrum for 2 in the coordinating
solvents mixture (CD3OD/D2O/DMSO-d6) shows the pres-
ence of two species (Table 1). The signal at δ 37.5 with
1J(195Pt,31P) of 2596 Hz is due to complex 2 (55 %) and the
two signals at δ -5.5 and 43.1 integrating by 2P and 4P
1
with J(195Pt,31P) couplings of 3130 Hz (P trans to N) and
2568 Hz (P trans to P), respectively evidence the formation
of the diplatinum compound [Pt2(PNHP)3]I4 (2a) (45 %).
This complex contains two PNHP ligands involving the
three donor atoms in the coordination to the platinum and
A
the third aminophosphine bridges the two PtNP2 centres
through the PB atoms (Scheme 1).
Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084
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M. I. Garcıa-Seijo, A. Habtemariam, D. Fernandez-Anca, S. Parsons, M. E. Garcıa-Fernandez
Table 1 31P {1H} NMR data for complexes 1Ϫ7 and reactions
δPa)
Solvent
1J(195Pt, 31P)
1
37.9s
37.0s
CDCl3
CDCl3
1 ϩ 2 eq. AuI
2
2
33.2s
37.5s[2P] (2)
Ϫ5.5s[2P], 43.1s[4P] (2a)
Ϫ6.6s[2P], 41.7s[4P]
Ϫ1.1s[2P], 33.9bs[4P]b) (2aЈ)
0.9bs[2P], 19.9s[2P]b), 28.6s[2P]b) (2aЉ)
33.8s[2P] (2)
CDCl3
CD3OD/D2O/DMSO-d6
2625
2596
3130, 2568
3114,2594
2343b)
2aЈ
CDCl3
CD2Cl2/CH3OH
2 ϩ 2 eq. Au(tdg)Cl
1610b), 2630b)
2614
2 ϩ 2 eq. AuI
CDCl3/CD2Cl2
Ϫ0.9s[1P], 42.1s[1P], 45.4s[2P] (2b)
Ϫ5.9t[2P], 43.2d[4P]b),c) (2a*)
46.1 [2P] (2c)
2 ϩ 6 eq. AgNO3
2 ϩ 3 eq. AcCysSHd)
CD3OD/D2O/DMSO-d6
CD3OD/D2O/DMSO-d6
2564b)
2582
35.5s[2P] (2)
2591
Ϫ7.1bs[2P], 41.9d[4P]b),c) (2a)
2589b)
2 ϩ 6 eq. AgNO3
ϩ 3 eq. AcCysSHd)
48.1s[2P]
CD3OD/D2O/DMSO-d6
CD3OD/D2O/DMSO-d6
2531
3130, 2297
2586
Ϫ5.2t[2P], 44.5d[4P]c) (2a*)
35.5s (2)
2 ϩ 3 eq. GSHd)
37.5de)
Ϫ7.0s[2P], 40.9d[4P]c) (2a)
3.5s[1P], 36.0s[2P]
Ϫ4.4bs[1P], 27.6bs[2P]
36.4s[2P]b), 37.7s[1P] (4a)
36.9bs[2P]b), 38.1bs[1P] (4b)
Ϫ26.5bs[1P], 34.4s[2P]
Ϫ26.8bs[1P], 2.2s[2P]
Ϫ4.0bs[2P], 40.1s[1P]
18.7s[1P], 33.6s[2P]
32.2s[1P], 33.8s[2P]
3
4
CD2Cl2
DMSO-d6
DMSO-d6/D2O
DMSO-d6/D2O
CDCl3
3726, 2597
2719b)
4 ϩ 2 eq. AcCysSHd)
4 ϩ 2 eq. GSHd)
2831b)
5
6
7
CDCl3
CDCl3
b)
d)
a) [Relative intensities: nP]. δ/1J(195Pt, 31P). c) 2J(31P, 31P) ϭ 20 Hz. pH ϭ 3.0-4.5. e) 2J(31P, 31P) ϭ 11 Hz
showing signals at δ Ϫ1.1 and 33.9 integrating by 2P and 4P
atoms, respectively due to [Pt2(PNHP)3]Cl4 (2aЈ) and three
resonances at δ 0.9, 19.9 and 28.6 integrating for 2P in each
case attributable to an potential isomer 2aЉ (Eq. (1)).
3[Pt(PNHP)I]I ϩ 6Au(tdg)Cl
(2)
Ǟ
(1)
ᎏᎏᎏᎏᎏ
CD2Cl2/CH3OH
[Pt2(PNHP)3]Cl4 ϩ 6Au(tdg)I ϩ PtCl2
(2aЈ, 2aЉ)
The 1J(195Pt,31P) value of 1610 Hz for the signal at δ 19.9
suggests a five-coordination of platinum (2aЉ) in accordance
with the proposed structure of Figure 2. The signal at
downfield for 2aЉ was attributed to PA atoms in a square-
planar arrangement [1J(195Pt,31P) ϭ 2630 Hz, P trans to P]
while the signals at δ 19.9 and 0.9 can be attributed to PAЈ
and (PB, PBЈ), respectively the PAЈ and PBЈ atoms being in-
volved in a trigonal-bipyramidal geometry.
Figure 1 31P {1H} NMR spectra for: (a) [Pt(PNHP)I]I (2) in
CDCl3, (b) [Pt2(PNHP)3]Cl4 (2aЈ) in CDCl3, (c) [Pd(NP3)I]I (3) in
CD2Cl2, (d) PdAu(NP3)I3 (7) in CDCl3. For atom labelling see
Schemes 1 and 2 and Figure 2.
Complex 2aЈ containing the same cation as 2a (Scheme
1) was isolated as a solid and its 31P {1H} NMR spectrum
in CDCl3 is shown in Figure 1b. This spectrum unequivo-
cally confirms the presence of two aminophosphines coord-
inating in a tridentate chelating fashion (PA) and the third
acting as a PP-bridging ligand (PB), the coupling constants
Reactions of complexes 1Ϫ4
Reactions with metal salts. While complex 1 retains its struc-
ture in solution by addition of AuI (Table 1) showing the
absence of interaction, complex 2 reacts with Au(tdg)Cl and
AuI to form diplatinum and heterobimetallic complexes,
respectively. The addition of two equivalents of Au(tdg)Cl
to 2 in CD2Cl2/CH3OH leads to a 31P {1H} NMR spectrum
1
1J(195Pt,31PA) ϭ 2594 Hz and J(195Pt,31PB) ϭ 3114 Hz be-
ing characteristic of P trans to P and P trans to N, respec-
tively.
In spite of the higher inertness of platinum complexes
compared to the analogous of palladium the reaction be-
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Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084

Cationic Palladium(II) and Platinum(II) Iodo Complexes
Figure 2 Structures proposed in solution for the cation
[Pt2(PNHP)3]4ϩ of 2aЉ, [PtAu(PNHP)2I]I2 (2b), PdCu(NP3)I3 (two
isomers of 5), PdAg2(NP3)I4 (6) and PdAu(NP3)I3 (two isomers
of 7).
Figure 3 Molecular Structure of 1
tween [Pt(PNHP)I]I and AuI in CDCl3/CD2Cl2 seems to
occur in some extent (Table 1). Besides the signal due to
1
the precursor 2 at δ 33.8 with J(195Pt,31P) ϭ 2614 Hz there
appeared three singlets at δ Ϫ0.9, 42.1 and 45.4 with inte-
gration ratios 1:1:2 suggesting the formation of the heterob-
imetallic complex [PtAu(PNHP)2I]I2 (2b). The structure
proposed for 2b (Figure 2) is in agreement with an assig-
nation of the signal at downfield to PA and the signals at δ
42.1 and Ϫ0.9 to PBЈ and PB, respectively.
The formation of the nitrate derivative [Pt(PNHP)-
(ONO2)](NO3) (2c) coexisting with [Pt2(PNHP)3](NO3)4
(2a*) (Table 1) requires the interaction of 2 with excess
AgNO3 (Eq. (2), cs ϭ coordinating solvents).
4[Pt(PNHP)I]I ϩ 6AgNO3 cǞs [Pt (PNHP) ](NO )
(2)
ᎏ
2
3 4
(2)
(2a*3)
ϩ [Pt(PNHP)(ONO2)](NO3) ϩ 6AgIȇ ϩ Pt(cs)2I2
(2c)
Figure 4 Molecular Structure for the cation of 3a
Copper(I), silver(I) and gold(I) are able to induce a che-
late ring-opening of 3 with formation of the heterobimetal-
lic complexes PdCu(NP3)I3 (5), PdAg2(NP3)I4 (6) and
PdAu(NP3)I3 (7). The 31P {1H} NMR spectra of 5 and 7
are different to that of the precursor 3 (Figure 1c) and re-
veal the presence of two isomers. The signals at δ 34.4 (5)
and 33.6 (7, Figure 1d) can be attributed to the axial PG
atoms of the distorted trigonal-bipyramidal centre for the
neutral isomer (Figure 2) and the resonances at δ -26.5 and
18.7 to the PH atoms of the PMЈI fragments (MЈ ϭ Cu,
Au). The second isomer seems to be neutral and ionic for 5
and 7, respectively in accordance with conductivity meas-
urements. The resonances at δ 2.2 (5) and 33.8 (7) can be
assigned to the PL and PE atoms of the neutral and cationic
distorted square-planar palladium centres for 5 and 7,
respectively, the signals at higher field δ -26.8 (5) and 32.2
(7) corresponding to the linear PMЈI moieties [PH (MЈ ϭ
Cu), PF (MЈ ϭ Au)].
signed to the PM atom involved in a five-membered chelate
ring around palladium. The conductivity measurements
also support this proposal of a neutral complex in solution.
Reactions with thiols. The interaction of 2 with thiols
such as AcCysSH or GSH in a 1:3 stoichiometric ratio
(Table 1) gives the dinuclear species 2a coexisting with unre-
acted complex 2. The signal at δ 37.5 for the reaction (2 ϩ
3GSH) atributable to the thiolate adduct was not observed
in the same process involving AcCysSH. Likewise from the
reaction (2 ϩ 3AcCysSH) in the presence of 6 eq. of
AgNO3 is difficult to evidence the Pt-thiol interaction.
However, complex 4 interacts with these thiols in (DMSO-
d6/D2O) (Table 1), undergoing a chelate ring-opening with
spontaneous oxidation of one P atom of NP3, to give com-
pounds 4a (AcCysSH) and 4b (GSH) (Scheme 2). The res-
onances at δ 37.7 (4a) and 38.1 (4b) were assigned to the
PFϭO groups and the signals at δ 36.4 (4a) and 36.9 (4b)
The two signals found in the 31P {1H} NMR spectrum
of 6 in CDCl3 at δ -4.0 and 40.1 with integration ratio 2:1
are consistent with the structure proposed in Figure 2. The
signal at higher field corresponds to PN atoms of the linear
PAgI fragments while the resonance at δ 40.1 can be as-
1
with J(195Pt,31P) values of 2719 and 2831 Hz, respectively
were attributed to PE trans to PE involved in the two fused
five-membered chelate rings.
Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084
1079

´
´
´
´
M. I. Garcıa-Seijo, A. Habtemariam, D. Fernandez-Anca, S. Parsons, M. E. Garcıa-Fernandez
Table 2 Summary of crystal parameters, data collection and refinement for 1 · H2Oa) and 3aa)
1 · H2O
C28H31I2NP2OPd
819.68
150(2)
3a
Empirical formula
Formula weight/gmolϪ1
T/K
C84H84I6N2P6Pd3
2387.95
150(2)
˚
λ/A
0.71073 (Mo)
0.28 ϫ 0.25 ϫ 0.21
yellow/ block
monoclinic
P21/c
18.601(5)
11.413(3)
14.934(4)
90
111.06(2)
90
2958.5(13)
4
0.71073 (Mo)
0.48 ϫ 0.20 ϫ 0.19
orange/block
triclinic
Crystal size/mm
Colour/habit
Crystal system
Space group
¯
P1
˚
a/A
11.3850(13)
12.8047(15)
15.4113(18)
94.7940(10)
104.128(2)
100.585(2)
2122.1(4)
1
˚
b/A
˚
c/A
Ͱ/°
β/°
γ/°
3
˚
V/A
Z
Calculated density/Mg mϪ3
Absorption coefficient/mmϪ1
F(000)
1.840
2.844
1584
1.869
2.968
1148
θ range for data collection/°
Reflections collected
Independent reflections
Max. and min. transmission
Data/restraints/parameters
Goodness of fit on F2
Final R indices
2.73 to 25.03
5214
5212 [Rint ϭ 0.0332]
0.133/0.188
5212/0/317
1.022
R1 ϭ 0.0482
wR2 ϭ 0.1287
I > 2σ (I)
2.631/Ϫ1.299
1.38 to 28.91
19097
9936 [Rint ϭ 0.0210]
1/0.626
9936/0/457
1.005
R1 ϭ 0.0269
wR2 ϭ 0.0663
I > 2σ (I)
1.223/Ϫ0.603
Criterion for observation
Largest diff. peak and hole (e A
Ϫ3
˚
)
a)
Crystallographic data for the structures have been deposited with the Cambridge Crystallographic Data Centre, CCDC 176099 and CCDC 176100. Copies
of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: int.codeϩ(1223)336-033;
e-mail for inquiry: fileserv@ccdc.cam.ac.uk; e-mail for deposition: deposit@ccdc.cam.ac.uk).
˚
Solid state structures of 1·H2O and 3a: X-ray
crystallography
Table 3 Selected distances/A and angles/° for complexes 1 · H2O
and 3a
Perspective views of the molecular structures and number-
ing schemes of complexes 1 · H2O and 3a are shown in
Figures 3 and 4. A summary of crystal structure param-
eters, data collection and refinement is given in Table 2, and
selected bond lengths and angles are listed in Table 3.
Palladium(II) exhibits a distorted square-planar ge-
ometry in both complexes 1 · H2O and 3a. The aminophos-
phine PNHP in 1 · H2O is a tridentate chelating ligand
bound through the three donor atoms (PNP) and the fourth
coordination site is occupied by an iodide. A second iodide
is the counteranion. The structural arrangement for 1 · H2O
is the same as that found for [Ni(PNHP)Cl]Cl [4] and anal-
ogous to [Pt(triphos)X]X (X ϭ Cl, Br, I) [21].
1 · H2O
3a
Pd(1)-P(1)
Pd(1)-P(2)
Pd(2)-P(3)
Pd(2)-P(3a)
Pd(1)-N(1)
Pd(1)-I(1)
Pd(2)-I(2)
Pd(2)-I(2a)
P(2)-Pd(1)-P(1)
P(3)-Pd(2)-P(3a)
N(1)-Pd(1)-P(1)
N(1)-Pd(1)-P(2)
P(2)-Pd(1)-I(1)
P(1)-Pd(1)-I(1)
P(3)-Pd(2)-I(2)
P(3)-Pd(2)-I(2a)
P(3a)-Pd(2)-I(2a)
P(3a)-Pd(2)-I(2)
N(1)-Pd(1)-I(1)
I(2a)-Pd(2)-I(2)
2.2961(2)
2.2948(2)
2.3069(7)
2.2802(7)
2.3415(7)
2.3415(7)
2.114(2)
2.5757(4)
2.5863(3)
2.5863(3)
170.06(3)
180.00(2)
86.14(6)
2.093(5)
2.5912(8)
164.98(7)
84.58(2)
83.60(2)
95.38(5)
96.61(5)
84.75(6)
93.38(2)
96.011(2)
93.069(2)
86.931(2)
93.069(2)
86.931(2)
175.10(6)
180.000(2)
˚
The Pd-N bond length [2.093(5) A] is slightly higher than
˚
the same distances for [Pd(PNHP)X]X [X ϭ Cl, 2.061(5) A;
˚
178.48(2)
X ϭ Br, 2.070(5) A] in consistence with the higher trans
effect of iodo over chloro and bromo ligands [15,22]. On
the other hand, the smaller trans influence of the nitrogen
over the phosphorus produces a Pd-I bond distance
˚
[2.5912(8) A] shorter than for the triphos complex [Pd(tri-
˚
phos)I]I [2.665(2) A] [23]. The Pd-P distances [2.2961(2),
The coordination sphere for palladium is tetrahedrally
distorted from planar arrangement, with the two phos-
phorus atoms on one side (0.099/0.101 A) of the least-
˚
2.2948(2) A] are close to values given in the literature for
other PdII complexes with two mutually trans ϪPPh2 moiet-
˚
ies [24].
squares plane defined by [P(1), P(2), N(1), I(1)] and with
1080
Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084

Cationic Palladium(II) and Platinum(II) Iodo Complexes
˚
˚
the nitrogen (0.120 A) and the iodine (0.079 A) atoms on
· H2O. The trans-PdI2P2 centres show I-Pd-I angles of 180°
and P-Pd-I angles slightly above [93.069(2)°] and less
[86.931(2)°] than 90°.
˚
the opposite side. The palladium atom is displaced 0.081 A
from the least-squares plane and to the same side as the
nitrogen and iodine atoms.
The N-Pd-I angle is 178.48(2) A which is close to the
ideal 180°. In contrast, the P-Pd-P angle is found to be only
164.98(7) A, probably as a result of ring strain in the triden-
˚
Conclusions
˚
Iodide is a better hydrogen bonding acceptor site for N-H
in [Pd(PNHP)X]X complexes than chloride or nitrate and
behaves similarly to the bromide. The iodo complex
[Pt(PNHP)I]I is mononuclear while the chloro and bromo
complexes are dinuclear compounds of the type
[Pt2(PNHP)3]X4. While PtII and PNHP favoured the forma-
tion of dinuclear compounds, PdII and NP3 allowed the ob-
tention of crystals of the unusual trinuclear ionic complex
[Pd3(NP3)2I4]I2. Although [Pd(PNHP)I]I does not react
with AuI the platinum derivative seems to react and form a
heterobimetallic compound. Complex [Pd(NP3)I]I reacts
with MЈI (MЈ ϭ Cu, Ag, Au) salts to obtain heterobimetal-
lic compounds. The formation of PtII-thiolate adducts was
only observed quantitatively for interactions between thiols
and the iodide derivative of NP3.
tately bonding PNP ligand. The small P-Pd-N angles for
the two adjacent five-membered chelate rings [83.60(2)°,
84.58(2)°] also display the strained coordination geometry
of the rings, as generally observed in five-membered phos-
phine chelate rings [25]. In this case, the ethylene chains of
the ligand adopt a boat conformation (Figure 3) which was
also previously observed for [Pd(PNHP)Br]Br and which is
absent in [Pd(PNHP)X]X (X ϭ Cl, NO3). Furthermore, 1 ·
˚
H2O shows N-H···I bonds of 2.850 A involving the I coun-
teranion. This type of short interactions were also found
˚
for the bromo derivative (N-H···Br, 2.371 A) while were not
observed in [Pd(PNHP)X]X (X ϭ Cl, NO3) [15]. The short
contacts can be explained as a consequence of the greater
trans effect of iodo and bromo over chloro or oxygen of
Ϫ
NO3 which allows the approach of the counteranions to
the N-H bonds. On the other hand, the presence of a water
molecule in the opposite side of the iodo ligand also leads
to short iodo counteranion-oxygen and carbon(6)-oxygen
Experimental Part
General Procedures. Diphenylphosphine, potassium tetrachloropla-
tinate(IV) and palladium(II) chloride were purchased from Strem
Chemicals, potassium tert-butoxide, 2,2Ј-thiodiethanol and bis(2-
chloroehyl)amine hydrochloride from Aldrich, tris(2-chloroethyl)-
amine hydrochloride from Acros and sodium chloride and iodide
from Panreac. THF was dried over Na and freshly distilled before
use. Microanalyses were performed on a Fisons Instrument EA
1108 CHNS-O. Fast Atom Bombardment (FAB) mass spectra were
obtained in a Micromass Autospec spectrometer using nitro-
benzylic alcohol as the matrix. Conductivities were measured at
25 °C using 10Ϫ3 M solutions in DMF or CH3CN on a WTW
model LF-3 instrument. Infrared spectra were recorded at ambient
temperature as KBr pellets (4000Ϫ500 cmϪ1) or Nujol mulls
(500Ϫ100 cmϪ1) on a Mattson Cygnus 100 spectrophotometer. The
bands are reported as s ϭ strong, m ϭ medium, w ϭ weak, sh ϭ
shoulder, b ϭ broad. 31P {1H} NMR spectra were recorded on a
Bruker DMX500 NMR spectrometer at 202.46 MHz. Chemical
shifts (δ) are reported in ppm relative to external 85 % H3PO4. The
signals are reported in Table 1 as s ϭ singlet, d ϭ doulet and bs ϭ
broad signal.
˚
contacts (3.630 and 3.375 A, respectively). The value of
˚
C(6)ϪH···O bond was found to be 2.414 A.
The X-ray crystal structure of 3a is made up of
[Pd3(NP3)2I4]I2 units consisting of trinuclear dications
[Pd3(NP3)2I4]2ϩ (Figure 4) and iodide anions. The cations
contain two distorted square-planar PdNP2I centres with
NP3 acting as tridentate chelating ligand through the nitro-
gen and two phosphorus atoms and forming two fused five-
membered chelate rings at palladium. The remaining phos-
phorus of each ligand are bound to a PdI2 fragment in a
trans-PdI2P2 arrangement there being this palladium atom
the centre of symmetry of each cation. As far as we know
this is the first example of a crystal structure for a NP3
compound with two types of square-planar metal centres.
Likewise, there is not described in the literature any other
crystal structure for a tripalladium(II) complex of NP3.
˚
˚
˚
The Pd-N [2.114(2) A], Pd-I [2.5757(4) A] and Pd-P
˚
[2.2802(7) A, 2.3069(7) A] bond distances in the square-
planar PdNP2I centres are very close to those found for 1
· H2O with identical arrangement at palladium. The Pd-I
Syntheses and titrations
˚
˚
[2.5863(3) A] and Pd-P [2.3415(7) A] bond lengths in the
trans-PdI2P2 centre are slightly greater than the analogous
distances in the PdNP2I centres.
Au(tdg)Cl. Solutions of AuI were prepared by treating Au with HCl
and HNO3 in an oil bath (120 °C) and reduction from AuIII to
AuI with 2,2Ј-thiodiethanol (thiodiglycol) as it was indicated in the
literature [17,26,27].
The deviation of the palladium atom from the least-
squares plane defined by [P(1), P(2), N(1), I(1)] is of
Synthesis of PNHP. Bis[2-(diphenylphosphino)ethyl]amine (PNHP)
was prepared as an air-stable hydrochloride (PNHP.HCl) [11,12].
Diphenylphosphine (14 ml, 15.0 g, 80.4 mmol) was added to a sus-
pension of potassium tert-butoxide (23.4 g, 208.5 mmol) in dry
THF (450 ml) under argon. The resulting deep red solution was
stirred for 20 min and bis(2-chloroethyl)amine hydrochloride (7.1 g,
40.0 mmol) was added as a powder. The mixture was refluxed for
28 h at 80 °C and after that a 1 M solution of HCl (ca. 100 ml)
˚
0.009 A. This deviation together with deviations of phos-
˚
phorus atoms (0.078/0.082 A) on the same side and of nitro-
˚
gen and iodine (0.094/0.066 A) on the opposite side are a
consequence of the slight tetrahedral distortion from the
planar geometry.
The N-Pd-I [175.10(6)°] and P-Pd-P [170.06(3)°] angles
for the PdNP2I centres reveal a lower ring strain than in 1
Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084
1081

´
´
´
´
M. I. Garcıa-Seijo, A. Habtemariam, D. Fernandez-Anca, S. Parsons, M. E. Garcıa-Fernandez
was added. After removing the solvents a white solid precipitated
40 %, mp 175 °C. Found: C, 50.1; H, 4.8; N, 2.0. Calc. For
and was dried in vacuo. It was recrystallised from CH2Cl2/ether and
washed with CH3CN. Yield: 60 %, mp 155 °C. Calc. for
C28H30NP2Cl: C, 70.4; H, 6.3; N, 2.9. Found for C28H30NP2Cl
(PNHP.HCl): C, 70.1; H, 6.4; N, 3.0 %.
C86H91N3P6Pt2Cl8: C, 49.5; H, 4.5; N, 2.0 %.
MS (FAB): m/z ϭ 1077 (Mϩ - 4Cl Ϫ PNHP -Pt, 8 %); 636 (Mϩ - 4Cl
Ϫ2PNHP -Pt, 23 %). 31P {1H} NMR (CDCl3): See Table 1. Λ(CH3CN) ϭ
131.7 ohmϪ1cm2molϪ1
.
31P {1H} NMR (CDCl3): δP -22.7s. IR: νmax/ cmϪ1 (N-H) 3300. MS (FAB):
Synthesis of [Pd(NP3)I]I (3). This complex was obtained as dihy-
drate 3·2H2O. A suspension of PdCl2 (0.1358 g, 0.7657 mmol) and
NaCl (0.0895 g, 1.5314 mmol) in CH3OH (25 ml) was heated on a
water bath (80 °C) until a clear solution was obtained. This was
allowed to cool to ambient temperature and NaI (0.4591 g,
3.0628 mmol) was added as a powder. Inmediately a solution of
NP3 (0.5000 g, 0.7657 mmol) in CH2Cl2 (20 ml) was added drop-
wise and the reaction mixture was stirred for 5 h at room tempera-
ture. Solvents were partially removed in vacuo untill an orange
brown solid started to precipitate. Then ether was added to com-
plete the precipitation of the complex which was filtered off and
washed with H2O. Solid was recrystallised in CH2Cl2/ether and
dried in vacuo. Yield: 85 %, mp > 250 °C. Found: C, 48.1; H, 4.6;
N, 1.4. Calc. For C42H46NO2P3PdI2: C, 48.0; H, 4.4; N, 1.3 %.
m/z ϭ 442 (Mϩ, 100 %).
Synthesis of NP3. Tris(2-diphenylphosphinoethyl)amine (NP3) was
prepared as free amine [10b,13]. Diphenylphosphine (11 ml, 11.8 g,
62.9 mmol) was added to a suspension of potassium tert-butoxide
(18.1 g, 160.9 mmol) in dry and freshly distilled THF (250 ml) un-
der argon. The resulting deep red solution was stirred for 15 min
and tris(2-chloroethyl)amine hydrochloride (5.0 g, 20.8 mmol) was
added as a powder. The mixture was refluxed for 20 h at 80 °C,
poured into 700 ml of water and cooled in an ice bath. The ligand
precipitated and was filtered off, recrystallised from DMF/H2O and
washed with ethanol. Yield: 78 %, mp 102 °C. Anal. Calc. for
C42H42NP3: C, 77.1; H, 6.5; N, 2.1. Found: C, 77.1; H, 6.9; N,
2.1 %.
IR νmax /cmϪ1 (Pd-I) 185m. MS (FAB): m/z ϭ 886 (Mϩ - I, 100 %); 759
31P {1H} NMR (CDCl3): δ -22.7s.
(Mϩ - 2I, 6 %).31P {1H} NMR (CD2Cl2): See Table 1. Λ(CH3CN) ϭ
134.2 ohmϪ1cm2molϪ1
.
Synthesis of [Pd(PNHP)I]I (1). Complex 1 was isolated as 1·H2O.
Synthesis of [Pd3(NP3)2I4]I2 (3a). Methanol (ca. 8 ml) was added to
a solution of [Pd(NP3)I]I·2H2O (0.010 g, 0.0095 mmol) in CH2Cl2
(10 ml) and the final solution was filtered. Orange crystals suitable
for X-ray diffraction were obtained after the solution had stood at
ambient temperature for some days.
A
suspension of PdCl2 (0.0743 g, 0.4188 mmol) and NaCl
(0.0489 g, 0.8376 mmol) in H2O (15 ml) was heated on a water bath
(80 °C) until a clear solution was obtained. This was allowed to
cool to ambient temperature and NaI (0.2511 g, 1.6752 mmol) was
added as a powder. Inmediately a solution of PNHP.HCl (0.2000 g,
0.4188 mmol) in CH2Cl2 (16 ml) was added dropwise and the mix-
ture reaction was stirred for 15 h at room temperature. After that
the organic phase was extracted with CH2Cl2, dried over anhidrous
Na2SO4, filtered and solvent removed in vacuo to leave dark red
solid. By recrystallization from CH2Cl2/n-hexane, yellow crystals
suitable for X-ray diffraction were obtained. Yield: 71 %, mp
239 °C. Found: C, 40.9; H, 3.8; N, 1.7. Calc. For C28H31NOP2PdI2:
C, 40.9; H, 3.8; N, 1.7 %.
Synthesis of [Pt(NP3)I]I (4). The compound was obtained as dihy-
drate 4·2H2O. To a solution of K2PtCl4 (0.1907 g, 0.4594 mmol) in
H2O (20 ml) NaI (0.2754 g, 1.3964 mmol) was added as a powder.
Inmediately a solution of NP3 (0.3000 g, 0.4594 mmol) in CH2Cl2
(12 ml) was added dropwise and the reaction mixture was stirred
for 5 h at room temperature. After that CH2Cl2 was extracted in
vacuo to leave a yellow solid which was filtered off, washed with
methanol and dried in vacuo. Yield: 73 %, mp 217 °C. Found: C,
44.5; H, 4.3; N, 1.0. Calc. For C42H46NO2P3PdI2: C, 44.3; H, 4.1;
N, 1.2 %.
IR νmax/cmϪ1 (Pd-I) 190s. MS (FAB): m/z ϭ 673 (Mϩ Ϫ I, 100 %); 547 (Mϩ
Ϫ
2I, 10 %). 31P {1H} NMR (CDCl3): See Table 1. Λ(CH3CN)
ϭ
116.8 ohmϪ1cm2molϪ1
.
IR νmax /cmϪ1 (Pt-I) 151s. MS (FAB): m/z ϭ 974 (Mϩ - I, 16 %); 848 (Mϩ
2I, 3 %).31 {1H} NMR (DMSO-d6): See Table 1. Λ(DMF)
64.6 ohmϪ1cm2molϪ1
-
ϭ
P
Synthesis of [Pt(PNHP)I]I (2). This compound was prepared as the
ether solvate 2·1.5(CH3CH2)2O. To solution of K2PtCl4
.
a
(0.1449 g, 0.3491 mmol) in H2O (16 ml) NaI (0.2318 g,
1.3964 mmol) was added as a powder. Inmediately a solution of
PNHP.HCl (0.2500 g, 0.5236 mmol) in CH2Cl2 (18 ml) was added
dropwise and the reaction mixture was stirred for 14 h at room
temperature. After that the organic phase was extracted with
CH2Cl2, dried over anhydrous Na2SO4 and filtered. Solvent was
partially removed in vacuo and n-hexane was added to precipitate
the light yellow solid which was filtered off and dried in vacuo.
Yield: 72 %, mp 172 °C. Found: C, 40.9; H, 4.1; N, 1.5. Calc. For
C34H44NO1.5P2PtI2: C, 40.8; H, 4.4; N, 1.4 %.
Synthesis of PdCu(NP3)I3 (5). This complex was prepared as
5·1.5H2O. To solution of [Pd(NP3)I]I·2H2O (0.1600 g,
a
0.1524 mmol) in dry CH2Cl2 (30 ml) CuI (0.0336 g, 0.1764 mmol)
was added as a solid and the reaction mixture was stirred under
nitrogen in an ice bath for 24 h. After that an orange solid precipi-
tated. Ether was added to complete the precipitation and the solid
formed was filtered off and dried in vacuo. Yield: 86 %, mp >
250 °C. Found: C, 41.5; H, 3.9; N, 1.2. Calc. For
C42H45NO1.5P3PdCuI3: C, 41.2; H, 3.6; N, 1.1 %.
IR νmax /cmϪ1 (Pd-I) 176s; (Cu-I) 159sh. MS (FAB): m/z ϭ 1074 (Mϩ - I,
3 %); 885 (Mϩ - 2I - Cu, 64 %); 759 (Mϩ - 3I - Cu, 2 %).31P {1H} NMR
IR νmax /cmϪ1 (Pt-I) 151s. MS (FAB): m/z ϭ 762 (Mϩ Ϫ I, 27 %); 636 (Mϩ
(CDCl3): See Table 1. Λ(CH3CN/DMF) ϭ 40.6/26.5 ohmϪ1cm2molϪ1
.
Ϫ
2I, 4 %). 31P {1H} NMR (CDCl3): See Table 1. Λ(CH3CN)
ϭ
121.8 ohmϪ1cm2molϪ1
.
Synthesis of PdAg2(NP3)I4 (6). The complex was prepared as dihy-
drate 6·2H2O. AgI (0.0695 g, 0.2958 mmol) was added as a solid
to a solution of [Pd(NP3)I]I·2H2O (0.1500 g, 0.1429 mmol) in
CH2Cl2 (35 ml) and the mixture was stirred for 24 h in the absence
of light. The solution was filtered, concentrated to a small volume
and ether was added to precipitate a yellow solid which was filtered
off and dried in vacuo. Yield: 69 %, mp > 180Ϫ182 °C. Found: C,
32.9; H, 3.3; N, 0.9. Calc. For C42H46NO2P3PdAg2I4: C, 33.2; H,
3.1; N, 0.9 %.
Synthesis of 2a (See Table 1).
Synthesis of [Pt2(PNHP)3]Cl4 (2aЈ). This complex was isolated as
the solvate 2aЈ·2CH2Cl2. To a solution of K2PtCl4 (0.1449 g,
0.3491 mmol) in H2O (16 ml) a solution of PNHP (0.2500 g,
0.5236 mmol) in CH2Cl2 (18 ml) was added dropwise and the reac-
tion mixture was stirred for 22 h. After that the organic phase was
extracted with CH2Cl2, dried over anhidrous Na2SO4 and filtered.
Solvent was partially removed in vacuo and n-hexane was added to
precipitate the solid which was filtered off and dried in vacuo. Yield:
MS (FAB): m/z ϭ 885 (Mϩ - 3I - 2Ag, 6 %). 31P {1H} NMR (CDCl3): See
Table 1. Λ(DMF) ϭ 21.5 ohmϪ1cm2molϪ1
.
1082
Z. Anorg. Allg. Chem. 2002, 628, 1075Ϫ1084

Cationic Palladium(II) and Platinum(II) Iodo Complexes
Synthesis of PdAu(NP3)I3 (7). The compound was prepared as the
solvate 7·4CH2Cl2. To a solution of [Pd(NP3)I]I·2H2O (0.1200 g,
0.1054 mmol) in CH2Cl2 (35 ml) AuI (0.0383 g, 0.1183 mmol) was
added as a solid and the reaction mixture was stirred under nitro-
gen in an ice bath for 2 h during which a solution was obtained. It
was filtered and partially concentrated in vacuo and ether was ad-
ded to precipitate a brown solid, which was filtered off and dried
in vacuo. Yield: 52 %, mp 162 °C (dec.). Found: C, 32.9; H, 3.3; N,
0.9. Calc. For C46H50NP3PdAuCl8I3: C, 32.9; H, 3.0; N, 0.8 %.
Thornton-Pett, J. Chem. Soc., Dalton Trans. 1994, 3311. (c) O.
Serindag, R. D. W. Kemmitt, J. Fawcett, D. Russell, Transition
Met. Chem. 1999, 24, 486.
[6] P. L. Orioli, C. A. Ghilardi, J. Chem. Soc. (A) 1970, 1511.
´
´
´
[7] M. I. Garcıa-Seijo, M. E. Garcıa-Fernandez, A. Habtemar-
iam, P. del S. Murdoch, R. O. Gould, P. J. Sadler, 34th ICCC,
Edinburgh, Scotland, U.K. 2000, P. Abs. P0939.
[8] (a) F. Cecconi, C. A. Ghilardi, S. Midollini, A. Orlandini, In-
org. Chem. Commun. 1999, 2, 275. (b) F. Cecconi, C. A. Ghil-
ardi, S. Midollini, S. Moneti, A. Orlandini, G. Scapacci, J.
Chem. Soc., Dalton Trans. 1989, 211.
IR νmax /cmϪ1 (Pd-I) 189w. MS (FAB): m/z ϭ 1208 (Mϩ - I, 10 %); 885
(Mϩ - 2I - Au, 4 %).31P {1H} NMR (CDCl3): See Table 1. Λ(CH3CN) ϭ
116.8 ohmϪ1cm2molϪ1
.
[9] (a) C. A. Ghilardi, S. Midollini, S. Moneti, A. Orlandini, G.
Scapacci, A. Traversi, J. Chem. Soc., Dalton Trans. 1990, 2293.
(b) F. Cecconi, C. A. Ghilardi, S. Midollini, S. Moneti, A.
Orlandini, G. Scapacci, Inorg. Chim. Acta 1991, 189, 105.
[10] (a) M. M. Taqui Khan, E. Rama Rao, Polyhedron 1987, 6,
1727. (b) M. M. Taqui Khan, E. Rama Rao, Polyhedron 1988,
7, 29.
[11] L. Sacconi, R. Morassi, J. Chem. Soc. (A) 1968, 2997.
[12] M. E. Wilson, R. G. Nuzzo, G. M. Whitesides, J. Am. Chem.
Soc., 1978, 100, 2269.
Titrations of 1 and 2 with gold group metal salts and of 2 and 4
with thiols
Solutions of AgNO3 in CD3OD, Au(tdg)Cl in CH3OH or AuI as
solid were added to a solution of complex 2 in CD2Cl2 or solutions
of 1 and 2 in CDCl3 and CDCl3/CD2Cl2, respectively achieving
different stoichiometric ratios. After 12 h the 31P {1H} NMR spec-
trum was recorded.
The same procedure was followed for titrations of 2 (CD3OD/
DMSO-d6) and 4 (DMSO-d6) with ACysSH and GSH in D2O.
[13] L. Sacconi, I. Bertini, J. Am. Chem Soc. 1968, 90, 5443.
The details of the experimental conditions for titrations resulting
in the formation of 2aЉ, 2b, 2c, 4a and 4b are described in Table 1.
´
[14] M. I. Garcıa-Seijo, Ph. D. Thesis, Univ. Santiago de Compost-
ela 2000.
´
[15] M. I. Garcıa-Seijo, A. Habtemariam, S. Parsons, R. O. Gould,
´
´
M. E. Garcıa-Fernandez, New J. Chem. (accepted).
X-ray crystallography
[16] W. J. Geary, Coord. Chem. Rev. 1971, 7, 81.
Table 2 summarises the crystal data, data collection, structural
solution and refinement parameters for complexes 1 · H2O and 3a.
A yellow block of 1 · H2O and an orange block of 3a were mounted
on glass fibers and used for data collection. Crystal data were col-
lected at 150(2) K using a Stoe Stadi4 four-circle diffractometer
equipped with an Oxford Cryosystem variable temperature device
for 1 · H2O and a Bruker SMART CCD area detector dif-
fractometer for 3a. Graphite monochromated Mo-Kα radiation
was used throughout for data collection. A psi-scans [28] and a
SADABS [29] absorption correction was made for 1 · H2O and
3a, respectively.
[17] P. Sevillano, A. Habtemariam, S. Parsons, A. Castin˜eiras, M.
´
E. Garcıa, P. J. Sadler, J Chem Soc, Dalton Trans. 1999, 2861.
[18] (a) R. M. Silverstein, G. C. Bassler, T. C. Morril, Spectrometric
Identification of Organic Compounds, 4th edn., John Wiley &
Sons, New York 1981. (b) L. M. Harwood, C. J. Moody and
J. M. Percy, Experimental Organic Chemistry, 2nd edn.,
Blackwell Science Ltd., U. K. 1999.
[19] K. Nakamoto, Infrared and Raman Spectra of Inorganic and
Coordination Compounds, 5th edn., John Wiley & Sons, New
York 1997.
´
´
´
[20] (a) M. I. Garcıa-Seijo, M. E. Garcıa-Fernandez, Recent Re-
search Developments in Inorganic and Organometallic Chemis-
try. Review Article on Polyphosphine Complexes, Ed. Re-
Structures of 1 · H2O and 3a were solved by Patterson (DIRDIF)
[30]. The structures were refined by full-matrix least-squares tech-
niques on F2 using the program SHELXL-97 [31]. Hydrogen atoms
were placed geometrically and positional parameters were refined
using a riding model. Hydrogen atoms of water molecules were not
placed for 1 · H2O. Atomic scattering factors were obtained with
the use of International Tables for X-ray crystallography [32]. Mo-
lecular graphics were obtained from SHELXTL.
´
search Signpost 2001 (in press). (b) M. I. Garcıa-Seijo, D. Fer-
´
´
´
´
´
nandez, S. Parsons, M. E. Garcıa-Fernandez, Reunion Cientıf-
´
ica de Bioinorganica, Miraflores de la Sierra (Madrid), Spain
2000, P. Abs. P.25.
[21] (a) C. E. Housecroft, B. A. M. Shaykh, A. L. Rheingold, B.
S. Haggerty, Acta Cryst. 1990, C46, 1549. (b) P. Sevillano, A.
´
Habtemariam, A. Castin˜eiras, M. E. Garcıa, P. J. Sadler, Poly-
Acknowledgement. Grants for M.I.G.S. (Xunta de Galicia, Spain)
are gratefully acknowledged.
´
hedron 1998, 18, 383. (c) P. Sevillano, M. E. Garcıa, Fourth
International Meeting on Gold and Silver in Medicine, Mil-
waukee, USA 1998, P. Abs. P-116.
´
´
[22] D. Fernandez, P. Sevillano, M. I. Garcıa-Seijo, A. Castin˜eiras,
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