Synthesis and coordination studies of new aminoalcohol functionalized tertiary phosphines

Article abstract of DOI:10.1139/v01-037

The synthesis of two new aminoalcohol functionalized tertiary phosphines o-Ph₂PCH₂N(H)C₆H₄(OH) (I) and o-Ph₂PCH₂N(H)C₆H₄(CH ₂OH) (II) are reported. Oxidation with aqueous H₂O₂ gave the corresponding phosphine oxides o-Ph₂P(O)CH₂N(H)C₆H₄ (OH) (III) and o-Ph₂P(O)CH₂N(H)C₆ H₄(CH₂OH) (IV) (³¹P NMR evidence only). The ligating ability of I, II and, in several cases, the known ligand 2,3-Ph₂PCH₂N(H)C₅H₃N(OH) (V), was investigated with a range of late transition-metal precursors. Accordingly, reaction of 2 equiv of I (or II) with [MCl₂(cod)] (M = Pd or Pt, cod = cycloocta-1,5-diene) gave the corresponding dichloro metal(II) complexes [MCl₂(I)₂] (M = Pd 1; M = Pt 2) and [MCl₂(II)₂] (M = Pd 3; M = Pt 4) in which I (and II) P-coordinate. Solution NMR studies reveal that 2 and 4 are exclusively cis whereas 1 and 3 are present as a mixture of cis and (or) trans isomers [4.7:1 (for 1); 2.2:1 (for 3)]. Reaction of 2 equiv of II with [Pt(CH₃)₂(cod)] gave the neutral complex [Pt(CH₃)₂(II)₂] (5) whose X-ray structure confirmed a cis disposition of "hybrid" ligands. In contrast, reaction of I with [Pt(CH₃)₂(cod)] gave initially [Pt(CH₃)₂(I)₂] (6) which, upon standing, afforded several products possibly reflecting an increased acidity of the phenolic groups of ligated I. Chloro bridge cleavage reactions of [{Ru(μ-Cl)Cl(p-cymene)}₂] or [{Rh(μ-Cl)Cl{C₅(CH₃)₅}}₂] with I (or II) proceeds smoothly and gave the mononuclear complexes [RuCl₂(p-cymene)I] (7), [RuCl₂(p-cymene)II] (8), [RhCl₂{C₅(CH₃)₅}I] (9), and [RhCl₂{C₅(CH₃)₅}II] (10) in good yield. X-ray crystallography confirms both ruthenium complexes bear P-coordinated I (or II) ligands. Molecules of 7 are linked into linear chains via O-H···Cl_coord intermolecular hydrogen bonding, a feature absent in the closely related compound 8. Reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with 1 equiv of I (or II) gave the corresponding gold(I) complexes [AuCl(I)] (11) and [AuCl(II)] (12). Bridge cleavage of the cyclometallated palladium(II) dimers [{Pd(μ-Cl)(C～N)}₂] [C～N = C,N-C₆H₄CH₂N(CH₃)₂, C,N-C₁₀H₆N(CH₃)₂, C,N-C₆H₄N=NC₆H₅] with V (or I) gave the neutral complexes [PdCl(C～N)V] (13-15) (or [PdCl(C₉H₁₂N)I] (16)), respectively. Chloride abstraction from 13 (or 15) with Ag[BF₄] gave the cationic complexes [Pd(C～N)V][BF₄] (17) (or 18) in which V P,N_pyridyl-chelates to the palladium(II) metal centre. The X-ray structures of 13 and 18 have been determined and confirm the expected coordination environments. An array of intra- and intermolecular H-bonding contacts are also observed. All compounds have been characterized by a combination of spectroscopic and analytical studies.

Full text of DOI:10.1139/v01-037

780
Synthesis and coordination studies of new
aminoalcohol functionalized tertiary phosphines
Sean E. Durran, Martin B. Smith, Alexandra M.Z. Slawin, Thomas Gelbrich,
Michael B. Hursthouse, and Mark E. Light
Abstract: The synthesis of two new aminoalcohol functionalized tertiary phosphines o-Ph2PCH2N(H)C6H4(OH) (I) and
o-Ph2PCH2N(H)C6H4(CH2OH) (II) are reported. Oxidation with aqueous H2O2 gave the corresponding phosphine ox-
ides o-Ph2P(O)CH2N(H)C6H4(OH) (III) and o-Ph2P(O)CH2N(H)C6H4(CH2OH) (IV) (31P NMR evidence only). The li-
gating ability of I, II and, in several cases, the known ligand 2,3-Ph2PCH2N(H)C5H3N(OH) (V), was investigated with
a range of late transition-metal precursors. Accordingly, reaction of 2 equiv of I (or II) with [MCl2(cod)] (M = Pd or
Pt, cod = cycloocta-1,5-diene) gave the corresponding dichloro metal(II) complexes [MCl2(I)2] (M = Pd 1; M = Pt 2)
and [MCl2(II)2] (M = Pd 3; M = Pt 4) in which I (and II) P-coordinate. Solution NMR studies reveal that 2 and 4 are
exclusively cis whereas 1 and 3 are present as a mixture of cis and (or) trans isomers [4.7:1 (for 1); 2.2:1 (for 3)]. Re-
action of 2 equiv of II with [Pt(CH3)2(cod)] gave the neutral complex [Pt(CH3)2(II)2] (5) whose X-ray structure con-
firmed a cis disposition of “hybrid” ligands. In contrast, reaction of I with [Pt(CH3)2(cod)] gave initially [Pt(CH3)2(I)2]
(6) which, upon standing, afforded several products possibly reflecting an increased acidity of the phenolic groups of
ligated I. Chloro bridge cleavage reactions of [{Ru(µ-Cl)Cl(p-cymene)}2] or [{Rh(µ-Cl)Cl{C5(CH3)5}}2] with I (or II)
proceeds smoothly and gave the mononuclear complexes [RuCl2(p-cymene)I] (7), [RuCl2(p-cymene)II] (8),
[RhCl2{C5(CH3)5}I] (9), and [RhCl2{C5(CH3)5}II] (10) in good yield. X-ray crystallography confirms both ruthenium
complexes bear P-coordinated I (or II) ligands. Molecules of 7 are linked into linear chains via O-H···Clcoord
intermolecular hydrogen bonding, a feature absent in the closely related compound 8. Reaction of [AuCl(tht)] (tht =
tetrahydrothiophene) with 1 equiv of I (or II) gave the corresponding gold(I) complexes [AuCl(I)] (11) and [AuCl(II)]
(12). Bridge cleavage of the cyclometallated palladium(II) dimers [{Pd(µ-Cl)(C~N)}2] [C~N = C,N-C6H4CH2N(CH3)2,
C,N-C10H6N(CH3)2, C,N-C6H4N=NC6H5] with V (or I) gave the neutral complexes [PdCl(C~N)V] (13–15) (or
[PdCl(C9H12N)I] (16)), respectively. Chloride abstraction from 13 (or 15) with Ag[BF4] gave the cationic complexes
[Pd(C~N)V][BF4] (17) (or 18) in which V P,Npyridyl-chelates to the palladium(II) metal centre. The X-ray structures of
13 and 18 have been determined and confirm the expected coordination environments. An array of intra- and
intermolecular H-bonding contacts are also observed. All compounds have been characterized by a combination of
spectroscopic and analytical studies.
Key words: phosphines, crystal structures, alcohols, precious metals. 791
Résumé : On a réalisé la synthèse de deux nouvelles phosphines tertiaires fonctionnalisées par un aminoalcool,
o-Ph2PCH2N(H)C6H4(OH) (I) et o-Ph2PCH2N(H)C6H4(CH2OH) (II). Leur oxydation par du peroxyde d’hydrogène
aqueux conduit aux oxydes de phosphines correspondantes, o-Ph2P(O)CH2N(H)C6H4(OH) (III) et o-
Ph2P(O)CH2N(H)C6H4(CH2OH) (IV) (uniquement démontré par RMN du 31P). On a étudié l’habilité des composés 1
et 2 et, dans plusieurs cas, du ligand bien connu 2,3-Ph2PCH2N(H)C5H3N(OH) (V), d’agir comme coordinats pour
une variété des précurseurs contenant des métaux de transition lourds. En conséquence, la réaction de deux équiv de
I (ou II) avec du [MCl2(cod)] (M = Pd ou Pt, cod = cycloocta-1,5-diène) conduit à la formation de complexes dic-
hlorométalliques [MCl2(I)2] (M = Pd 1; M = Pt 2) et [MCl2(II)2] (M = Pd 3; M = Pt 4) dans lesquels les phosphi-
nes I (et II) sont coordinées au phosphore. Des études de RMN en solution révèlent que les composés 2 et 4
existent exclusivement sous la forme cis alors que les composés 1 et 3 existent sous la forme de mélanges
d’isomères cis/trans [4,7:1 pour 1 et 2,2:1 pour 3]. La réaction de deux équiv de II avec le [Pt(CH3)2(cod)] conduit
à la formation du complexe neutre [Pt(CH3)2(II)], 5, dont la structure telle que déterminée par diffraction des rayons
X confirme la présence d’une disposition cis des ligands hybrides. Par opposition, la réaction de I avec le
[Pt(CH3)2(cod)] conduit initialement à la formation de [Pt(CH3)2(I)2], 6, qui laissé à lui-même conduit à la formation
Received October 10, 2000. Published on the NRC Research Press Web site at http://canjchem.nrc.ca on July 9, 2001.
This article is dedicated to Brian James on the special occasion of his 65th birthday.
S.E. Durran and M.B. Smith.1 Department of Chemistry, Loughborough University, Loughborough, Leics, LE11 3TU U.K.
A.M.Z. Slawin. School of Chemistry, University of St. Andrews, St Andrews, Fife, KY16 9ST U.K.
T. Gelbrich, M.B. Hursthouse and M.E. Light. EPSRC X-Ray Crystallography Service, Department of Chemistry, University of
Southampton, Highfield, Southampton, SO17 1BJ U.K.
1Corresponding author (telephone: +44 (0)1509 222553; fax: +44 (0)1509 213925; e-mail: m.b.smith@lboro.ac.uk).
Can. J. Chem. 79: 780–791 (2001)
DOI: 10.1139/cjc-79-5/6-780
© 2001 NRC Canada

Durran et al.
781
de plusieurs produits et ceci est vraisemblablement un reflet d’une augmentation de l’acidité des groupes phénoli-
ques de la phosphine (I) qui est liée. Les réactions de clivage du pont chloro du [{Ru(µ-Cl)Cl(p-cymène)}2] ou du
[{Rh(µ-Cl)Cl{C5(CH3)5}}2] avec I (ou II) se produisent facilement et conduisent à la formation de complexes mo-
nonucléaires [RuCl2(p-cymène)I], 7, [RuCl2(p-cymène)II], 8, [RhCl2l{C5(CH3)5}I], 9, et [RhCl2l{C5(CH3)5}II], 10
avec de bons rendements. La diffraction des rayons X permet de confirmer que les deux complexes du ruthénium
comportent des ligands I (ou II) qui sont coordinés au phosphore. Les molécules de 7 forment des chaînes linéaires
par le biais d’une liaison hydrogène intermoléculaire, O–H···Clcoord, une caractéristique qui est absente dans le com-
posé 8 qui lui est fortement apparenté. La réaction de [AuCl(tht)] (tht = tétrahydrothiophène) avec un équivalent de
I (ou II) conduit à la formation des complexes d’or correspondants [AuCl(I)], 11, et [AuCl(II)], 12. Le clivage du
pont des dimères cyclométallés du palladium [{Pd(µ-Cl)(C~N)}2] [C~N = C,N-C6H4CH2N(CH3)2, C,N-C10H6N(CH3)2
et C,N-C6H4N=NC6H5] à l’aide des phosphines V
(ou I) conduit respectivement à la formation des complexes neutres [PdCl(C~N)V], 13–15, ou [PdCl(C9H12N)I], 16.
L’enlèvement du chlorure à partir des composés 13 (ou 15) à l’aide de Ag[BF4] conduit à la formation des com-
plexes cationiques [Pd(C~N)V][BF4], 17 (ou 18) dans lesquels le P,N-pyridyl de la phosphine V se chélate au centre
métallique du palladium(II). Les structures des composés 13 et 18 ont été déterminées par diffraction des rayons X
et elles confirment les environnements attendus par la coordination. On a aussi observé un arrangement de contacts
par liaisons hydrogènes intra- et intermoléculaires. Tous les composés ont été caractérisés par une combinaison
d’études analytiques et spectroscopiques.
Mots clés : phosphines, structures cristallines, alcools, métaux précieux.
[Traduit par la Rédaction] Durran et al.
functionalized tertiary phosphines in which the connectivity
Introduction
between disparate P and O donors bears an additional nitro-
gen donor atom, itself potentially capable of metal
complexation. One interesting aspect we wished to probe
further is what hydrogen bonding motifs would be expected
upon coordination and accordingly, subtle variations in the
ligand structures described here enable such a comparison to
be tested. Previously we noted that Ph2PCH2N(H)C5H3N(X)
(X = H, OH) can adopt a range of H-bonding motifs (e.g.,
A–D) (15) and in this work, two new network arrangements
(E and F) are presented.
Tertiary phosphines continue to engage a quintessential
role in the development of many avenues of coordination
and organometallic chemistry and in catalysis. The ability to
modify a ligand structure, in a precise and controlled fashion,
explains the recent significant advances made in catalytic se-
lectivity and activity, facile catalyst separation and enhanced
enantiomeric excesses in asymmetric transformations.
Recent impressive progressions in the synthesis and
chemistry of new functionalized tertiary phosphines have
been made, one notable class are the so-called “hemilabile”
ligands (1). Alcohol functionalized tertiary phosphines (2–
10) which, in addition to a mismatch of “soft” and “hard”
donor centres, have several attractive attributes: (i) reactive
site(s) for further functionalization. The ligand Ph2PCH2OH
is an excellent precursor for tertiary phosphines containing
macrocycle (11), β-cyclodextrin (12), chitosan (13), or even
dendrimer (14) backbones. Recently, we (15) prepared a
hydroxy-functionalized pyridylphosphine while Faraone and
co-workers (16) described the synthesis and catalytic appli-
cations of new mixed phosphine-phosphonite ligands, in
both cases using Ph2PCH2OH as a convenient starting mate-
rial; (ii) the hard oxygen donor can further be utilized in
forming heterobimetallic complexes, e.g., Ph2PCH2OH can
function as a uninegative P,O-bridging ligand (17); (iii) the
presence of several hydroxy groups can render transition-
metal complexes water soluble. The groups of Pringle
(18,19), Katti (20), and more recently Fukuoka (21) made
extensive use of this unique property in various coordina-
tion, catalytic, and biomedical studies.
Experimental
Chemicals
All reactions were performed under nitrogen unless other-
wise stated. The starting materials [MCl2(cod)] (M = Pd, Pt)
(25, 26), [Pt(CH3)2(cod)] (27), [{Ru(µ-Cl)Cl(p-cymene)}2]
(28), [{Rh(µ-Cl)Cl{C5(CH3)5}}2] (29), [AuCl(tht)] (30), and
[{Pd(C~N)(µ-Cl)}2] (C~N = C9H12N, C12H12N, C12H9N2)
(31) were prepared according to previous reported proce-
dures.
The
ligands
Ph2PCH2OH
(32)
and
Ph2PCH2N(H)C5H3N(OH) (15) were synthesized according
to known literature methods. The compounds o-
H2NC6H4(OH) and o-H2NC6H4(CH2OH) were purchased
from Aldrich Chemical Co. and used directly without further
purification.
Physical techniques and methods
Infrared spectra were recorded as KBr pellets in the range
4000–220 cm–1 on a PerkinElmer System 2000 Fourier
1
As part of an ongoing programme, we reported (15) the
transform spectrometer. H NMR spectra (250 MHz) were
synthesis and characterization of
a
new alcohol
recorded on a Bruker AC250 FT spectrometer with chemical
shifts (δ) in ppm to high frequency of SiMe4 and coupling
constants (J) in Hz. 31P NMR spectra (36.2 MHz) were re-
corded on a JEOL FX90Q spectrometer with chemical shifts
(δ) in ppm to high frequency of 85% H3PO4 and coupling
constants (J) in Hz. All spectra were measured in CDCl3 un-
less otherwise stated. Elemental analyses (PerkinElmer 2400
functionalized, potentially terdendate, pyridylphosphine and
demonstrated its suitability for further functional group in-
clusion. Herein we describe the synthesis of two new “hy-
brid” ligands and demonstrate their coordination capabilities
with selected precious metal precursors. To the best of our
knowledge, there are very few reports (22–24) of hydroxy-
© 2001 NRC Canada

782
Can. J. Chem. Vol. 79, 2001
N
N
H
PPh2
O
O
H
H
O
H
N
O
Cl
H
N
Ph2P
[M]
N
N
[M]
P
Ph2
N
Ph2P
N
H
Cl
A
C
B
N
N
[M]
N
[M]
OH
N
H
PPh2
OH
Cl
Ph2P
N
O
Cl
Ph2P
N
H
H
[M]
H
D
E
F
CHN Elemental Analyzer) were performed by the
Loughborough University Analytical Service within the De-
partment of Chemistry.
Using a similar procedure the following complexes were
prepared: [PdCl2{o-Ph2PCH2N(H)C6H4(OH)}2] (1) (93%),
[PtCl2{o-Ph2PCH2N(H)C6H4(OH)}2] (2) (72%), and
[PdCl2{o-Ph2PCH2N(H)C6H4(CH2OH)}2] (3) (68%).
Precious metal salts were provided on loan by Johnson
Matthey PLC.
[Pt(CH3)2{o-Ph2PCH2N(H)C6H4(CH2OH)}2] (5)
Ligand syntheses
To the solids [Pt(CH3)2(cod)] (0.025 g, 0.075 mmol) and
II (0.048 g, 0.149 mmol) was added toluene (ca. 1 mL) and
the solution left to stand. After ca. 12 d crystalline 5 was
isolated from solution (yield 0.038 g, 58%).
o-Ph2PCH2N(H)C6H4(CH2OH) (II)
To
a
solution of o-H2NC6H4(CH2OH) (0.286 g,
2.32 mmol) in CH3OH (5 mL) was added a solution of
Ph2PCH2OH (0.501 g, 2.23 mmol) in CH3OH (3 mL). After
stirring the solution for 30 min, toluene (13 mL) was added
and the solution heated at ca. 65°C for 18 h. The solution
was evaporated to dryness under reduced pressure and
triturated with several portions of petroleum ether (bp 40–
60°C). The solid was collected by suction filtration and dried
in vacuo. (yield 0.36 g, 48%). A similar method was used
for the synthesis of o-Ph2PCH2N(H)C6H4(OH) (I) (53%)
from o-H2NC6H4(OH).
[RuCl2(p-cymene){o-Ph2PCH2N(H)C6H4(OH)}] (7)
To the solids [{Ru(µ-Cl)Cl(p-cymene)}2] (0.100 g,
0.163 mmol) and o-Ph2PCH2N(H)C6H4(OH) (0.100 g,
0.326 mmol) was added CH2Cl2 (20 mL) and the deep red
solution stirred for 15 min. The solvent was reduced in vol-
ume to ca. 1 to 2 mL under reduced pressure and diethyl
ether (5 mL) added. The solid was isolated by suction
filtration and additional crops isolated from the filtrate
(yield 0.181 g, 91%). Using a similar procedure the
following compounds were prepared: [RuCl2(p-cymene){o-
Ph2PCH2N(H)C6H4(CH2OH)}] (8) (78%), [RhCl2{C5(CH3)5}{o-
Ph2PCH2N(H)C6H4(OH)}] (9) (90%), and [RhCl2{C5(CH3)5}{o-
Ph2PCH2N(H)C6H4(CH2OH)}] (10) (63%).
NMR reaction of aq H2O2 with (II)
To a CDCl3 (0.5 mL) solution of o-Ph2PCH2N(H)C6H4(CH2OH)
(0.020 g, 0.067 mmol) was added H2O2 (30% w/w, 0.1 mL)
and
a
31P NMR spectrum recorded. Only o-
Ph2P(O)CH2N(H)C6H4(CH2OH) IV was formed as inferred
by a new 31P NMR resonance of characteristic downfield
shift (δ (P) 30.9 ppm). In a similar manner we observed the
formation of o-Ph2P(O)CH2N(H)C6H4(OH) (III).
[AuCl{o-Ph2PCH2N(H)C6H4(OH)}] (11)
To a CH2Cl2 (ca. 5 mL) solution of [AuCl(tht)] (0.030 g,
0.094 mmol)) was added o-Ph2PCH2N(H)C6H4(OH)
(0.029 g, 0.094 mmol) and stirred for ca. 15 min. The vol-
ume was concentrated in vacuo to ~1 mL and petroleum
ether (bp 60–80°C, 20 mL) added. The solid was collected
by suction filtration and dried in vacuo (yield 0.035 g, 70%).
In a similar manner [AuCl{o-Ph2PCH2N(H)C6H4(CH2OH)}]
(12) was prepared (74%).
Complexes
[PtCl2{o-Ph2PCH2N(H)C6H4(CH2OH)}2] (4)
To a CH2Cl2 (10 mL) solution of [PtCl2(cod)] (0.050 g,
0.134 mmol) was added o-Ph2PCH2N(H)C6H4(CH2OH)
(0.089 g, 0.277 mmol). The solution turned immediately
deep yellow and progressively faded to pale yellow. After
ca. 15 min, solid 4 deposits from solution and was collected
by suction filtration and dried in vacuo (yield 0.094 g, 74%).
[PdCl(C12H12N){Ph2PCH2N(H)C5H3N(OH)}] (14)
To a CH2Cl2 (15 mL) solution of [{Pd(C12H12N)(µ-Cl)}2]
(0.099 g, 0.159 mmol) was added Ph2PCH2N(H)C5H3N(OH)
© 2001 NRC Canada

Durran et al.
783
(0.100 g, 0.324 mmol) as a solid. After stirring for ca. 1 h,
14 was filtered under reduced pressure and dried in vacuo
(yield 0.160 g, 81%). Using a similar procedure the following
for information on ordering electronically). Crystallographic
data (excluding structure factors) have also been deposited
with the Cambridge Crystallographic Data Centre as supple-
mentary publication no. CCDC 148 356 (5), 149 218 (7),
149 219 (8), 149 220 (13), and 148 357 (18) and can be ob-
tained, free of charge, on request from The Director, CCDC,
12 Union Road, Cambridge, CB2 1EZ, U.K. (Fax: 44-1223-
336033 or e-mail: deposit@ccdc.cam.ac.uk).
complexes
were
prepared:
[PdCl(C9H12N){Ph2-
PCH2N(H)C5H3N(OH)}] (13) (94%), [PdCl(C12H9N2){Ph2-
PCH2N(H)C5H3N(OH)}] (15) (91%), and [PdCl(C9H12N){o-
Ph2PCH2N(H)C6H4(OH)}] (16) (86%).
[Pd(C12H9N2){Ph2PCH2N(H)C5H3N(OH)-P,N}][BF4] (18)
To a CH2Cl2 (30 mL) suspension of Ag[BF4] (0.040 g,
Results and discussion
0.206
mmol)
was
added
[PdCl(C12H9N2){Ph2-
PCH2N(H)C5H3N(OH)}] (0.100 g, 0.158 mmol) and stirred,
in the dark, for ca. 2 h. The AgCl was removed by filtration
through a small Celite plug and reduced in vacuo to ca. 1 to
2 mL. Addition of diethyl ether (25 mL) gave 18 which was
collected by suction filtration and dried in vacuo (yield
0.086 g, 80%). In a similar manner [Pd(C9H12N){Ph2-
PCH2N(H)C5H3N(OH)P,N}][BF4] (17) (93%) was prepared.
Ligand syntheses
Reaction of Ph2PCH2OH (32) with commercially avail-
able aminoalcohols o-H2NC6H4(OH) and o-H2NC6H4(CH2OH)
in toluene–methanol at ca. 65°C for 18 h, gave after workup,
the new hybrid ligands o-Ph2PCH2N(H)C6H4(OH) (I) and o-
Ph2PCH2N(H)C6H4(CH2OH) (II), respectively, in reasonable
yields. A similar procedure was used recently for the prepa-
ration of the pyridyl analogue Ph2PCH2N(H)C5H3N(OH) (V)
(15). The 31P NMR spectra of I and II both displayed single
31P NMR resonances at ca. δ (P) –18 ppm, some 8 ppm up-
field of that observed for Ph2PCH2OH (δ (P) –9.9 ppm). One
feature noted upon monitoring the stability of these ligands,
when CDCl3 solutions are allowed to stand, is the formation
of a second new phosphorus species. Thus for I, after ca. 3 h,
a new species at δ (P) –25.6 ppm was observed and confidently
assigned as the diphosphine o-(Ph2PCH2)2NC6H4(OH). Inde-
pendently o-(Ph2PCH2)2NC6H4(OH) can be prepared by re-
action of o-H2NC6H4(OH) with 2 equiv of Ph2PCH2OH
under similar conditions.2 Other supporting data for I and II
are given in Tables 2 and 3.
X-ray Crystallography
Crystals of 5 were grown by allowing a toluene solution
of [Pt(CH3)2(cod)] and 2 equiv of II to stand for ca. 12 days.
For 7 and 8 suitable crystals for X-ray crystallography were
grown by slow diffusion of either Et2O (for 7) or petroleum
ether (bp 60–80°C) (for 8) into CDCl3 solutions over several
days. Suitable crystals of 13 were grown by slow diffusion
of Et2O into a CDCl3–CH3OH solution over 7 days whereas
for 18, X-ray quality crystals were obtained by allowing
CDCl3 solutions to stand for several days.
The crystal structures of compounds 7, 8, and 13 were ob-
tained using a Rigaku AFC7S serial diffractometer with
graphite-monochromated Mo Kα radiation (λ = 0.71069 Å)
and ω scans. Details of the crystal data collection and refine-
ment are given in Table 1. Intensities were collected by ω
scans over a single quadrant of reciprocal space. All data
were corrected for Lorentz polarization and long-term inten-
sity fluctuations. Absorption effects were corrected on the
basis of multiple equivalent reflections or by empirical
methods (33). Structures were solved by direct methods and
refined by full-matrix least-squares against F (teXsan) (34)
for data with I > 2σ(I). The weighting scheme used was as
previously reported (35). Refinements converged to residuals
given in Table 1. All calculations were made with programs
of the teXsan systems.
Data were collected (for 5 and 18) using a Nonius κ CCD
area detector diffractometer mounted at the window of a ro-
tating molybdenum anode. Ω scans were employed such that
95% of the unique data were recorded at least once. Data
collection and processing were carried out using the pro-
grams COLLECT (36), DENZO (37), and maXus (38) and
an empirical absorption correction was applied using
SORTAV (39, 40). The structures were solved via direct
methods (41) and refined by full-matrix least-squares (41)
on F2. Non-hydrogen atoms were refined anisotropically and
hydrogen atoms were treated using a riding model.
Oxidation of I (or II) with aq H2O2 proceeds smoothly af-
fording (as confirmed by 31P NMR spectroscopy, Table 3)
the corresponding tertiary phosphine oxides o-
Ph2P(O)CH2N(H)C6H4(OH) (III) and o-Ph2P(O)CH2N-
(H)C6H4(CH2OH) (IV).
H
N
H
N
Z
Z
P(E)Ph2
P(E)Ph2
CH2OH
OH
Z = CH, E = lone pair
Z = CH, E = O
Z = N, E = lone pair
I
Z = CH, E = lone pair
Z = CH, E = O
II
III
V
IV
Palladium(II) and platinum(II) chemistry
Reaction of 2 equiv of either I (or II) with [MCl2(cod)]
(cod = cycloocta-1,5-diene) gave the corresponding metal(II)
complexes [PdCl2(I)2] (1), [PtCl2(I)2] (2), [PdCl2(II)2] (3),
and [PdCl2(II)2] (4). Previously, we (15) showed that reac-
tion of 2 equiv of V with [PtCl2(cod)] gave the bis P,Npyridyl
chelate complex [Pt{Ph2PCH2N(H)C5H3N(OH)-P,N}2]Cl2.
The platinum(II) complexes 2 and 4 in solution have a cis
-
1
Copies of material on deposit may be purchased from The
Depository of Unpublished Data, Document Delivery,
CISTI, National Research Council Canada, Ottawa, ON
K1A 0S2, Canada (http://www.nrc.ca/cisti/irm/unpub_e.shtml
configuration as inferred by large J (Pt-P) coupling con-
stants (3678 Hz for 2, 3660 Hz for 4) whereas 1 and 3 are
present as a mixture of both cis and (or) trans isomers (4.7:1
(for 1); 2.2:1 (for 3)). For comparison the spectral data of
2 S.E. Durran and M.B. Smith. Unpublished work.
© 2001 NRC Canada

Table 1. Details of the X-ray data collections and refinements for compounds 5, 7, 8, 13, and 18.
Compound
5
7
8
13
18
Empirical Formula
MW
C42H46N2O2P2Pt C7H8
959.97
C29H32NOPCl2Ru
613.53
C30H34NOPClRu 0.5CHCl3
687.24
C27H29N3OPClPd 0.5CHCl3
644.06
C30H26N4OPPdBF4 H2O
700.74
Crystal system
Triclinic
Monoclinic
Monoclinic
Monoclinic
Monoclinic
Unit cell dimensions
a (Å)
b (Å)
c (Å)
α (°)
β (°)
γ (°)
11.2761(3)
11.8122(3)
16.7161(5)
103.9790(12)
96.4490(11)
91.8270(10)
2142.87(10)
150(2)
9.877(3)
16.430(3)
17.078(3)
11.041(3)
15.885(4)
35.394(7)
11.078(7)
26.974(4)
11.354(9)
10.4438(3)
9.5206(3)
14.6711(5)
93.64(3)
96.07(3)
115.76(4)
99.7840(10)
Volume (Å3)
Temperature (K)
Space group
Z
2766(1)
293(2)
P21/n
6173(3)
293(2)
P21/n
3055(3)
293(2)
P21/c
1437.55(8)
150(2)
P21
P-1
2
3.390
4
8
4
2
µ (mm–1)
0.829
0.887
0.902
0.764
Reflections collected
Independent reflections
19 755
8366
5358
5051
11 902
11 279
5798
5503
4758
3944
(R (int) = 0.0645)
R1 = 0.045,
wR2 = 0.085
2
(R (int) = 0.044)
R1 = 0.030,
wR1 = 0.027
(R (int) = 0.075)
R1 = 0.041,
wR1 = 0.043
(R (int) = 0.022)
R1 = 0.062,
wR1 = 0.075
[R(int) = 0.027]
R1 = 0.031,
wR2 = 0.077
Final R indices
(I > 2σ(I))a
aR = ∑ ||Fo| – |Fc||/∑ |Fo|. wR 2 = (∑ [w(Fo – Fc2)2]/∑ [w(Fo )2])1/2
2
.

Durran et al.
785
Fig. 1. Crystal structure of 5 (solvent omitted for clarity). Ther-
Table 2. Microanalytical dataa for compounds I, II, 1–5, and 7–18.
mal ellipsoids set at 50% probability level.
Analysis (%)
Compound
C
H
N
I
II
1
2
3
4
5b
7
8
9
10c
11
12
13
14
15
16
17
18
74.03 (74.24)
74.06 (74.74)
57.51 (57.62)
51.85 (51.82)
57.44 (58.59)
52.20 (52.86)
61.35 (61.30)
56.10 (56.77)
56.67 (57.42)
55.92 (56.51)
55.72 (55.75)
41.71 (42.28)
42.90 (43.38)
55.45 (55.48)
57.62 (58.07)
56.63 (57.06)
57.84 (57.64)
50.85 (51.01)
53.06 (52.77)
5.80 (5.92)
5.98 (6.29)
4.62 (4.59)
4.51 (4.13)
4.91 (4.92)
4.45 (4.45)
5.57 (5.68)
5.12 (5.26)
5.31 (5.46)
5.25 (5.40)
5.82 (5.45)
3.12 (3.36)
3.46 (3.64)
4.90 (5.01)
4.60 (4.72)
4.08 (4.16)
5.34 (5.19)
4.54 (4.61)
3.96 (3.85)
4.60 (4.56)
4.23 (4.36)
3.09 (3.54)
3.06 (3.18)
3.36 (3.42)
2.85 (3.08)
2.94 (2.92)
2.05 (2.28)
2.18 (2.23)
2.12 (2.27)
2.02 (2.15)
2.39 (2.60)
2.36 (2.53)
7.10 (7.19)
6.67 (6.77)
8.79 (8.87)
4.81 (4.80)
6.24 (6.61)
8.14 (8.21)
aCalculated values in parentheses.
bContains 1 mol toluene as solvate.
cContains 0.25 mol CH2Cl2 as solvate.
with II trans to a methyl group (43). The Pt-CH3 signals ap-
pear in the 1H NMR spectrum as phosphorus coupled
multiplets with 195Pt satellites (J (Pt-H) = 68.4 Hz). In con-
trast, reaction of 2 equiv of I with [Pt(CH3)2(cod)] in CDCl3
gave initially 6 which, upon standing at ambient temperature
for 20 h, gave a new major species tentatively assigned as
1–4 are similar to [MCl2{Ph2PCH2OH}2] (δ (P) 7.3 ppm,
1J (Pt-P) 3687 Hz, M = Pt (42); δ (P) 27.8 and
13.7 ppm, M = Pd (recorded in CH2Cl2–C6D6)). Further sup-
port comes from the IR spectra (KBr disc) of 2 and 4 which
display two νPtCl bands (Table 3). Apparently in the solid-
state only the cis isomer is observed for the palladium(II)
complexes 1 and 3.
1
trans-[Pt(CH3)Cl(I)2] (δ (P) 21.4 ppm, J (Pt-P) 3106 Hz).
After ca. 5 days the intensity of this species diminishes and
a new, as yet unidentified compound at δ (P) 22.9 ppm
(1J(Pt-P) 4469 Hz) is the major species present. Clearly, ei-
ther the acidity of the phenolic group of P-coordinated I or
residual traces of HCl (in CDCl3) may account for methane
elimination observed here. No attempts to identify methane
formation were pursued. Further reactivity studies are under-
way and will be reported in due course.
The X-ray structure of 5 (Fig. 1, Table 4) shows the ex-
pected near square-planar geometry (C(21)-Pt(1)-C(21′)
83.2(2)°, C(21)-Pt(1)-P(1) 86.84(15)°, C(21′)-Pt(1)-P(1′)
92.26(18)°, P(1)-Pt(1)-P(1′) 98.05(5)°) and comprises two
aminoalcohol functionalized tertiary phosphines and two
methyl ligands arranged in a cis configuration. The Pt—P
and Pt—C bond distances are comparable with those re-
cently reported (43) for [Pt(CH3)2(PR3)2] complexes. Hydro-
gen bonds involving both hydroxy groups of each molecule
result in a tetrameric (OH)4 eight-membered ring that con-
tain two intramolecular O(1)-H···O(1′) (O(1)···O(1′) 2.69 Å,
H···O(1′) 2.00 Å; O(1)-H…O(1′) 150°) and two
intermolecular O(1′)-H···O(1i) (where i = –x, –y, –z + 1;
O(1′)···O(1i) 2.76 Å, H···O(1i) 1.95 Å; O(1′)-H···O(1i) 169°]
interactions (Fig. 2). The two hydrogen bonded molecules in
each dimer are related by inversion symmetry. Additional
short intramolecular N(1)···O(1) and N(1′)···O(1′) contacts,
both in the range of 2.87 Å, show less favourable N-H···O
angles (113 and 128°), so we conclude they are probably the
result of steric restrictions rather than hydrogen bonds.
HO
Ph2
P
X
P
X
P
X
P
H
N
H
N
H
N
N
H
M
M
X
Ph2 Ph2
Ph2
OH
HO
OH
X = Cl, M = Pd
X = Cl, M = Pt
X = CH3, M = Pt
1a
2
X = Cl, M = Pd
1b
6
HO
Ph2
P
X
H
X
P
X
H
H
N
N
H
M
N
M
N
P
P
Ph2
X
Ph2 Ph2
OH
HO
OH
X = Cl, M = Pd
X = Cl, M = Pt
X = CH3, M = Pt
3a
4
X = Cl, M = Pd
3b
5
Reaction of 2 equiv of II with [Pt(CH3)2(cod)] in toluene
gave a white solid which analyzed, by microanalysis, as
[Pt(CH3)2(II)2].toluene (5 toluene). The 31P NMR spectrum
showed a single 31P NMR resonance at δ (P) 17.2 ppm, with
1
a considerably reduced J (Pt-P) of 1830 Hz and in keeping
© 2001 NRC Canada

786
Can. J. Chem. Vol. 79, 2001
Table 3. Selected spectroscopic data for compounds I–IV and 1–18.
J
δ (H)
(arom.)
IR
(νNH/OH
IR
(νC=N
δ (H) (CH2)a
Compound
δ (P)
(Pt-P)
J (Rh-P)
)
)
m/z
I
–18.8b
–18.5
32.2
30.9
26.3
14.2g
6.4
26.5
14.0g
5.8
7.52–6.61c
3.83 (3.7)
4.49, 3.86 (4.2)
3480, 3414, 3349
3479, 3386
307 (M)
321 (M)
II
III
IV
1
7.51–6.65c
7.82–6.47d,e
4.45 (5.8)
3380f
756 (M-Cl)
2
3
3678
7.57–6.53
7.82–6.58d,e
4.11
4.52, 4.28
3387h
3364, 3298f
845 (M-Cl)
785 (M-Cl)
4
5
6
7
8
3660
1830
1817
7.57–6.49e,i
7.54–6.41k
4.32 (5.1)j
4.46, 3.59
3369, 3293h
3384, 3309
908 (M)
867 (M)
17.2
17.4
23.9l
22.2
7.87–6.03m
7.86–6.24e,n
4.32 (6.5)
4.30 (5.1),
4.10 (5.3)
4.50
4.51, 4.41
4.26
4.57, 4.38
4.61 (3.7)
4.71 (4.8)
4.35
3418, 3245
3394
614 (M)
628 (M)
9
10
11
12
13
14
15
16
17
18
28.8
26.4
24.7l
30.2
34.5l
38.6l
33.7
34.2
33.2l
31.5
141
145
7.94–6.47o,p
7.97–6.45q
7.78–6.74
7.73–6.58p
7.87–6.30e,s
8.02–6.26e,t
8.06–6.04p
7.93–6.39u
7.70–6.42e,v
8.10–6.02w
3392, 3300
3396
3424, 3372r
3356r
3272
3326
3293, 3268
3383, 3275
3406, 3339
3409, 3361
616 (M)
630 (M)
539 (M)
1613
1611
1611
547 (M-Cl)
584 (M-Cl)
595 (M-Cl)
583 (M)
548 (M-BF4)
595 (M-BF4)
4.11
4.31
4.25 (4.6)
1624
1627
aJ (P-H) in parentheses.
bAfter ca. 3 h, a second species at δ (P) –25.6 ppm was observed.
cOther resonance at δ (H): 3.99 (NH) (for I), 4.90 (NH) (for II).
dOther resonances at δ (H): 9.46, 9.36 (OH); 4.87 (NH) (for 1); 5.36, 5.06 (NH–OH) (for 3).
eRecorded in (CD3)2SO.
fPdCl at 307 and 285 cm–1 (for 1); PdCl at 316 and 290 cm–1 (for 3).
gMixture of cis and (or) trans isomers, recorded in CDCl3–(CH3)2SO.
hPtCl at 311 and 284 cm–1 (for 2); PtCl at 318 and 293 cm–1 (for 4).
iOther resonances at δ (H): 5.35, 5.11 (NH–OH).
jOverlapping signals.
kOther resonances at δ (H): 5.14 (NH); 1.75 (OH); 0.58 (Pt-CH3), J (Pt-H) 68.4 Hz, J (P-H) 14.1 Hz.
lRecorded in CDCl3–CH3OH.
mOther resonances at δ (H): 9.03 (OH); 4.45 (NH): 5.49, 5.33, 2.32, 1.82, 0.77 [CH3C6H4{CH(CH3)2}].
nOther resonances at δ (H): 5.09, 4.85 (NH–OH); 5.51, 5.35, 2.33, 1.83, 0.79 [CH3C6H4{CH(CH3)2}].
oOther resonance at δ (H): 1.39 (J (P-H) 3.5 Hz, C5(CH3)5).
pδ (H) OH–NH not observed.
qOther resonances at δ (H): 5.25 (NH); 1.40 (J (P-H) 3.5 Hz, C5(CH3)5).
rAuCl at 322 cm–1 (for 11); 321 cm–1 (for 12).
sOther resonances at δ (H): 9.78 (OH); 6.17 (NH); 4.08 (J (P-H) 1.4 Hz, CH2), 2.75 (J (P-H) 2.1 Hz, N(CH3)2).
tOther resonances at δ (H): 9.67 (OH); 6.24 (NH); 3.43 (N(CH3)2).
uOther resonances at δ (H): 5.75 (OH); 4.76 (NH); 4.05 (J (P-H) 2.1 Hz, CH2), 2.86 (2.3 Hz, N(CH3)2).
vOther resonances at δ (H): 10.77 (OH); 7.30 (J (P-H) 13.7 Hz, NH); 4.11 (CH2); 2.54 (N(CH3)2).
wOther resonance at δ (H): 6.47 (J (P-H) 16.3 Hz, NH). OH not observed.
Other spectroscopic and microanalytical data (Tables 2 and
3) confirm the constitution of 7 and 8. The X-ray structures
of both ruthenium compounds have been determined
(Figs. 3 and 4, Table 5). Both molecules display similar
overall structures — pseudo-octahedral geometries at ru-
thenium comprising an η6-p-cymene, two chlorides and one
phosphorus bound ligand completing the metal coordina-
tion sphere. The Ru—Cl and Ru—P distances in 7 and 8
are similar (44), broadly as expected, and furthermore in
the case of 8 comparable to those values for [RuCl2(p-
Ruthenium(II), rhodium(III), and gold(I) chemistry
Reaction of I (or II) with [{Ru(µ-Cl)Cl(p-cymene)}2] in
CH2Cl2 at ambient temperature gave the mononuclear ru-
thenium complexes [RuCl2(p-cymene)I] (7) and [RuCl2(p-
cymene)II] (8). The 31P NMR spectra show, in both cases,
a single phosphorus resonance at δ (P) 23.9 (for 7) and 22.2
(for 8) ppm [cf. 16.3 ppm for [RuCl2(p-cymene)(Ph2PCH2OH)]
(G)]. Upon inspection of the coordination chemical shifts
(∆coord) (∆coord = 42.7 (for 7), 40.7 (for 8), 25.3 (for G)) we
observe a larger ∆coord for complexes bearing I and II.
© 2001 NRC Canada

Durran et al.
787
Fig. 2. Hydrogen bond interactions in 5.
Table 4. Selected bond distances (Å)
and angles (°) for compound 5.
Bond distances (Å)
5
Pt(1)—C(21)
Pt(1)—C(21′)
Pt(1)—P(1)
2.095(5)
2.116(5)
2.2849(13)
2.2817(14)
Pt(1)—P(1′)
Bond angles (°)
83.2(2)
C(21)-Pt(1)-C(21′)
C(21)-Pt(1)-P(1)
C(21′)-Pt(1)-P(1′)
P(1)-Pt(1)-P(1′)
86.84(15)
92.26(18)
98.05(5)
C(21′)-Pt(1)-P(1)
C(21′)-Pt(1)-P(1′)
168.67(17)
174.05(15)
also present which again are probably a consequence of
steric limitations. The related complex [RuCl(p-cy-
mene){Ph2PCH2N(H)C5H3N(OH)-P,N}]Cl exists in the
solid-state (15) as a dimer pair through simultaneous N-
H···Clanion and O-H···Clanion hydrogen bonding (D).
Fig. 3. Crystal structure of 7. Thermal ellipsoids set at 50%
probability level.
We also studied the reaction of I (and II) with the rho-
dium(III) precursor [{Rh(µ-Cl)Cl{C5(CH3)5}}2]. Chloro
bridge cleavage of [{Rh(µ-Cl)Cl{C5(CH3)5}}2] with I (and
II) in dichloromethane gave the rhodium(III) complexes
[RhCl2{C5(CH3)5}I] (9) and [RhCl2{C5(CH3)5}I] (10). The
31P and 1H NMR data are consistent with the proposed struc-
1
tures (Table 3). Hence δ (P) and J (Rh-P) for 9 (28.8 ppm,
141 Hz) and 10 (26.4 ppm, 145 Hz) are similar as expected.
1
In the H NMR spectra clear, well-resolved doublets at ca.
1.40 ppm (J (P-H) 3.5 Hz) confirm the presence of η5-li-
gated C5(CH3)5 ligands. The gold(I) complexes 11 and 12
were prepared from [AuCl(tht)] and 1 equiv of either I (or
II).
arene
arene
M
H
N
H
M
N
Cl
Cl
P
Ph2
Cl
Cl
P
Ph2
HO
HO
M = Ru
M = Rh
7
M = Ru
M = Rh
8
9
10
Cyclometallated palladium(II) chemistry
Treatment of the cyclometallated palladium(II) dimers
[{Pd(C~N)(µ-Cl)}2] [C~N = C9H12N, C12H12N, C12H9N2]
with 2 equiv of V gave the mononuclear complexes
[PdCl(C~N)V] (C9H12N (13), C12H12N (14), C12H9N2 (15))
in high yields (>80%) (Scheme 1). The 31P NMR spectra
(Table 3) of 13–15 show single 31P NMR resonance at δ (P)
34.5 (13), 38.6 (14), and 33.7 ppm (15) indicating similar
structures. We also prepared the related complex
[PdCl(C~N)I] 16 (C~N = C9H12N) whose 31P NMR reveals
a singlet at δ (P) 34.2 ppm indicating that pyridyl or phenyl
group inclusion has a marginal influence on δ (P). The trans
N-Pd-P geometry was inferred from the magnitude of the
J (P-H) couplings observed in the 1H NMR spectra (Table 3)
which correspond well with related compounds and by
X-ray crystallography. The X-ray structure of 13 (Fig. 5,
cymene){o-Ph2PCH2CH2C6H4(CH2OH)}] (5). In 7, mole-
cules are linked into one-dimensional chains through O-
H···Clcoord intermolecular hydrogen bonds (O(16)···Cl(1)
3.10 Å, H(16o)···Cl(1) 2.11 Å; O(16)-H(16o)···Cl(1) 162°).
Short intramolecular N···O contacts (N(14)···O(16) 2.62 Å,
H(14n)···O(16) 2.23 Å; N(14)-H(14n)···O(16) 100° for 7;
O(16)···N(14) 2.88 Å, H(16o)···N(14) 2.17 Å; O(16)-
H(16o)···N(14) 128° and O(46)···N(44) 2.87 Å,
H(46o)···N(44) 2.25 Å; O(46)-H(46o)···N(44) 143° for 8) are
© 2001 NRC Canada

788
Can. J. Chem. Vol. 79, 2001
Table 5. Selected bond distances (Å) and angles (°) for compounds 7 and 8.
Bond distances (Å)
7
8a
Ru(1)—l(1)
Ru(1)—Cl(2)
Ru(1)—P(1)
Ru(1)—Carene
2.424(2)
2.418(2)
2.351(1)
2.172(5)–2.247(5)
2.442(4)
2.400(3)
2.354(3)
2.18(1)–2.24(1)
(2.412(3))
(2.425(4))
(2.344(3))
(2.16(1)–2.23(1))
Bond angles (°)
Cl(1)-Ru(1)-Cl(2)
Cl(1)-Ru(1)-P(1)
Cl(2)-Ru(1)-P(1)
Cl(1)-Ru(1)-Carene
Cl(2)-Ru(1)-Carene
P(1)-Ru(1)-Carene
Carene-Ru(1)-Carene
88.12(6)
83.53(5)
86.11(5)
90.0(2)–157.4(2)
90.4(2)–156.0(2)
94.5(1)–159.0(2)
35.7(2)–80.5(2)
87.3(1)
86.6(1)
85.0(1)
88.5(3)–156.9(4)
91.9(4)–158.1(4)
93.5(3)–159.9(4)
35.6(5)–78.9(5)
(88.4(1))
(84.2(1))
(86.0(1))
(88.3(3)–157.6(4))
(89.2(4)–156.7(4))
(94.9(4)–161.1(4))
(35.5(4)–81.0(5))
aValues in brackets are the equivalent parameter in the second molecule.
Fig. 4. Crystal structure of 8 (solvent omitted for clarity). Ther-
Fig. 5. Crystal structure of 13 (solvent omitted for clarity). Ther-
mal ellipsoids set at 50% probability level.
mal ellipsoids set at 50% probability level.
cules are arranged into linear chains through O-H···Npyridyl
intermolecular H-bonding (O(16)···N(20A) 2.64 Å,
H(16o)···N(20A) 1.82 Å; O(16)-H(16o)···N(20A) 179°).
There is also an intramolecular N···O contact (N(14)···O(16)
2.64 Å, H(14n)···O(16) 2.09 Å; N(14)-H(14n)···O(16) 114°)
but like 5, 7, and 8 is probably not a legitimate H-bond.
Unlike complexes of I (or II) for which no further coordi-
nation studies were probed, reaction of 13 or 15 with
Ag[BF4] in dichloromethane gave the P,N-chelate complexes
Table 6) shows a near square-planar geometry around the
palladium(II) centre (N(21)-Pd(1)-C(25) 83.0(3)°, Cl(1)-
Pd(1)-N(21) 90.2(2)°, P(1)-Pd(1)-C(25) 92.9(3)°, and Cl(1)-
Pd(1)-P(1) 93.7(1)°) and comprises
a
chelating
cyclometallated C9H12N, a chloride, and a P-bound V
ligand. The P donor is trans to the dimethylamino group of
the cyclometallated ligand. The Pd—C, Pd—N, Pd—P, and
Pd—Cl distances are all broadly as anticipated (45). Mole-
[Pd(C~N){Ph2PCH2N(H)C5H3N(OH)}][BF4]
(C~N
=
C9H12N (17); C12H9N2 (18)). Slight upfield shifts were
© 2001 NRC Canada

Durran et al.
789
Fig. 6. Crystal structure of 18 (solvent and tetrafluoroborate anion omitted for clarity). Thermal ellipsoids set at 50% probability level.
Scheme 1. (i) 2 equiv V (or I), CH2Cl2; (ii) Ag[BF4], CH2Cl2.
Table 6. Selected bond distances (Å)
and angles (°) for compound 13.
Cl
N
C
C
N
Pd
Pd
Cl
Bond distances (Å)
13
Pd(1)—Cl(1)
Pd(1)—P(1)
Pd(1)—N(21)
Pd(1)—C(25)
2.386(3)
2.250(2)
2.139(7)
2.015(8)
(i)
OH
NH
N
Cl
H
N
Pd
Z
N
C
Z
(ii)
Bond angles (°)
C
Pd
P
Ph2
P
Ph2
83.0(3)
90.2(2)
92.9(3)
93.7(1)
173.2(3)
174.7(2)
N(21)-Pd(1)-C(25)
Cl(1)-Pd(1)-N(21)
P(1)-Pd(1)-C(25)
Cl(1)-Pd(1)-P(1)
Cl(1)-Pd(1)-C(25)
P(1)-Pd(1)-N(21)
HO
C~N = C9H12N, Z = N
C~N = C12H12N, Z = N
C~N = C12H9N2, Z = N
C~N = C9H12N, Z = CH
13
14
15
16
C~N = C9H12N, Z = N
C~N = C12H9N2, Z = N
17
18
observed in the 31P NMR spectra while the IR spectra
showed small (typically ca. 10–15 cm–1) downfield shifts in
νC=N(pyridyl) (Table 3). The X-ray structure of 18 (Fig. 6, Ta-
ble 7) confirms P,N-co-ordination of V with the pyridyl ni-
trogen trans to the orthometallated carbon. The Pd—N bond
lengths (Pd(1)-N(1) 2.098(3) Å (N trans to P) and Pd(1)-
N(4) 2.176(3) Å (N trans to C)) differ and reflect the higher
trans-influence of the aryl ligand compared to the tertiary
phosphine. The tetrafluoroborate and water molecules are al-
ternately linked via hydrogen bonds to form single chains
running along the 21 screw axis (Fig. 7 shows these hydro-
gen bonded chains viewed along the a axis, only the core of
the palladium complex is drawn). This involves both protons
on the water (H1W and H2W) and two of the
tetrafluoroborate fluorines (F2 and F3). The hydrogen bonds
formed are: O2-H1W···F2ii where ii = –x + 1, y + 0.5, –z
(O2···F2ii 2.72 Å, H1W···F2ii 2.14 Å; O2-H1W···F2ii 168°)
and O2-H2W···F3 (O2···F3 2.82 Å, H2W···F3 2.09 Å; O2-
H2W···F3 165°). The palladium complex is connected, in a
branch like manner, to these chains by a single hydrogen
© 2001 NRC Canada

790
Can. J. Chem. Vol. 79, 2001
Fig. 7. Hydrogen bonded chains in 18 (viewed along the a axis).
of 105.4° and is most likely imposed by the stereochemistry
and not a genuine hydrogen bond.
Acknowledgements
We should like to thank the EPSRC for funding and the
EPSRC Mass Spectrometry Service at Swansea. Johnson
Matthey are gratefully acknowledged for loans of precious
metals.
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