Cyclohexylbis(hydroxymethyl)phosphane: A hydrophilic phosphane capable of forming novel hydrogen-bonding networks

Article abstract of DOI:10.1002/ejic.200500823

The cyclohexyl-substituted (hydroxymethyl)phosphane CyP-(CH ₂OH)₂ (1) has been prepared by reaction of the corresponding primary phosphane CyPH₂ with aqueous formaldehyde. Compound 1 has been used as building block for the

Full text of DOI:10.1002/ejic.200500823

FULL PAPER
DOI: 10.1002/ejic.200500823
Cyclohexylbis(hydroxymethyl)phosphane: A Hydrophilic Phosphane Capable of
Forming Novel Hydrogen-Bonding Networks
Miriam Gonschorowsky,[b] Klaus Merz,[b] and Matthias Driess*[a]
Keywords: (Hydroxymethyl)phosphanes / Phosphane conjugates / Phosphane sulfides / Hydrogen bonds
The cyclohexyl-substituted (hydroxymethyl)phosphane CyP-
(CH2OH)2 (1) has been prepared by reaction of the corre-
sponding primary phosphane CyPH2 with aqueous formalde-
hyde. Compound 1 has been used as building block for the
synthesis of new functionalized water-soluble phosphorus
compounds. Thus, Mannich-type condensation of 1 with ex-
cess glycine affords the air-stable amino acid phosphane con-
jugate CyP[CH2N(H)CH2COOH]2 (2). Simple oxidation of 1
with hydrogen peroxide and elemental sulfur leads to the
crystalline chalcogenide derivatives CyP(O)(CH2OH)2 (3)
and CyP(S)(CH2OH)2 (4). X-ray diffraction analyses of the
latter revealed distinct intermolecular hydrogen bonding mo-
tifs and possess different types of hydrogen bond networks
to each other due to the different proton acceptor ability of
the chalcogen atom X of the P=X group (X = O, S): while the
oxygen atom of the P=O moiety in 3 serves as proton ac-
ceptor, affording a P=O–HO bifurcated network, the sulfur
atom of the P=S group denies hydrogen bonding interactions.
In addition, the ligand ability of 1 has been studied towards
Pt(+2) and Cu(+1) ions: Reaction of 1 with Pt(COD)Cl2 (COD
= cycloocta-1,5-diene) furnishes the air-stable complex cis-
[PtCl2{CyP(CH2OH)2}2] (5), while the crystalline dimeric
Cu(+1) complex [CuI{CyP(CH2OH)2}2]2 (6) results from the
reaction of CuI with two molar equivalents of 1. The complex
6 shows a intermolecular hydrogen bonding pattern different
from that of 1, 3 and 4, respectively. The new coordination
compounds 5 and 6 represent metal-phosphane labelled
alcohols which are promising building blocks for the synthe-
sis of metal-based drugs.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
of PH3 or organophosphanes, including oxidation reac-
tions,[1,2] nucleophilic substitution and addition reactions to
activated multiple bonds[1,3] or formation of phosphonium
salts via nucleophilic addition to alkylhalides.[2] Another
well established type of reactions of (hydroxymethyl)phos-
phanes represents the Mannich-type condensation with
amino-functionalized compounds like amines,[4] amino ac-
ids[5] or enzymes,[6] which leads to the formation of (ami-
nomethyl)phosphanes containing a ϾP–CH2–NϽ moiety.
As Henderson and co-workers have demonstrated, the
Mannich-type condensation is, for example, a feasible
method for the immobilization of phosphanes to amino-
functionalized polymer supports[7] and also render covalent
linkage of enzymes to insoluble supports by using multi-
functional (hydroxymethyl)phosphanes like P(CH2OH)3 as
coupling reagent.[6] Such immobilized supports are of high
interest for the development of a new class of catalysts,[6]
which may find diverse application, for imagine. In this con-
text, metal complexes of phosphane-derived biomolecules[8]
as well as the coordination chemistry of water-soluble (hy-
droxymethyl)phosphane ligands have attracted considerable
interest in the last decade for the design and development
of new water-soluble catalysts[9] or metal-based drugs.[8]
(Hydroxymethyl)phosphane ligands, especially the parent
system P(CH2OH)3, have been employed to synthesize
stable water-soluble complexes with catalytic active metals
Introduction
(Hydroxymethyl)phosphanes [P(CH2OH)xR3–x; R = H,
alkyl, aryl; x = 1, 2, 3] constitute an important class of
functionalized hydrophilic phosphanes, which have gained
considerable prominence in recent years. They are accessible
by insertion of formaldehyde into the P–H bonds of sec-
ondary and primary phosphanes or PH3 and combine the
chemical properties of common organophosphane donor li-
gands with that of hydrophilic alcohols. In other words,
such phosphanes are excellent precursors for the synthesis
of a variety of water-soluble organic and organometallic
phosphorus compounds. Since the P–CH2OH moieties can
easily be re-transformed into P–H bonds by liberation of
formaldehyde molecules, (hydroxymethyl)phosphanes can
be considered as masked primary or secondary organopho-
sphanes (RPH2, R2PH; R = alkyl, aryl) which are less sensi-
tive against air but more water-soluble in contrast to the
latter. Therefore (hydroxymethyl)phosphanes can partici-
pate in a number of chemical reactions, which are typical
[a] Institute of Chemistry: Metalorganics and Inorganic Materials,
Technical University Berlin, Sekr. C2,
Strasse des 17. Juni 135, 10623 Berlin, Germany
Fax: +49-30-314-22168
E-mail: matthias.driess@tu-berlin.de
[b] Faculty of Chemistry, Inorganic Chemistry I, University
Bochum,
Universitätsstrasse 150, 44801 Bochum, Germany
(e.g. Rh and Ir)[10] – for their use in biphasic catalysis[11]
–
Eur. J. Inorg. Chem. 2006, 455–463
© 2006 Wiley-VCH Verlag GmbH & Co. KgaA, Weinheim
455

M. Gonschorowsky, K. Merz, M. Driess
FULL PAPER
or with cytotoxic transition metals such as Pt and Au[12] for patent procedure,[18] by which 1 was obtained from the cor-
potential medical application. In addition, hydroxymethyl- responding phosphonium salt by treatment with a base at
functionalized phosphanes deserve not only attention as 50 °C. However, no data concerning characterization of 1
versatile phosphane ligands but also as versatile candidates were previously reported.
for crystal engineering studies. Especially multifunctional
bis(hydroxymethyl)phosphanes RP(CH2OH)2 and their
chalcogenide derivatives RP(X)(CH2OH)2 (X = O, S) ap-
pear as potential building blocks for different hydrogen
bonding pattern in solid state. However, there are only a
few examples known, demonstrating that (hydroxymethyl)
phosphanes and their chalcogenides[1] are able to form
intermolecular hydrogen bonds. To our surprise, structural
investigations are rather rare and only available for
(HOCH2)2P–CH2CH2–P(CH2OH)2,[13] ferrocenyl (Fc)-sub-
stituted (hydroxymethyl)phosphanes,[2,14,15] and their
derivatives FcP(X)(CH2OH)2 (X
=
O, S),[14,15]
FcCH2P(S)(CH2OH)2[2] and FcCH(CH3)P(S)(CH2OH)2,[16]
respectively. We report here the synthesis and characteriza-
tion of a variety of new cyclohexyl-derived bis(hydroxyme-
thyl) phosphane compounds. The versatile chemistry of the
readily accessible phosphane CyP(CH2OH)2 (1) is demon-
strated by several characteristic reactions, including Man-
nich-type condensation with glycine to form the amino acid
phosphane conjugate 2 and simple oxidation reactions of
the phosphorus atom with H2O2 and elemental sulfur, af-
fording the new phosphane chalcogenides CyP(X)-
(CH2OH)2 (3) (X = O) and 4 (X = S), respectively. Ad-
ditionally, initial studies on the coordination chemistry of
Scheme 1. Synthesis and reactions of CyP(CH2OH)2 1.
CyP(CH2OH)2 is an air-stable crystalline solid with an
ligand 1 were carried out towards Pt(+2) and Cu(+1) ions unpleasant odour, which is soluble in organic solvents as
which lead to the new complexes 5 and 6 and represent well as in water, due to its amphiphilic character. It was
metal-phosphane modified alcohols as potential precursors characterized by mass spectrometry, elemental analysis,
for metal-based drugs. In order to learn more about the NMR spectroscopy and X-ray diffraction analysis. The EI
molecular association of different bis(hydroxymethyl) phos- mass spectrum revealed the [M]+ peak at m/z = 176 (19%)
phorus moieties with and without P=X functions (X = O, and respective fragment ions due to the elimination of
S) via hydrogen bonds, the structures of 1, 3, 4 and 6 were formaldehyde and decomposition of the cyclohexyl group.
also established by X-ray diffraction analyses.
The 31P–NMR spectrum of 1 shows a broad singlet at δ =
–11.4 ppm similar to the chemical shifts observed for related
hydroxymethyl-functionalized phosphanes.[4] As expected,
1
Results and Discussion
the H-NMR spectrum of 1 reveals that the CH2 protons
of the PCH2OH groups are chemically inequivalent (dia-
stereotopic) and represent the AB part of an ABX spin sys-
Synthesis and Characterization of 1–6
All reactions described in this work, that include the tem (A, B = 1H; X = 31P). The inequivalence of the methyl-
preparation of the starting compound CyP(CH2OH)2 (1) as ene protons is caused by the pyramidally coordinated, pro-
well as the various syntheses performed with this precursor, chiral phosphorus center. Simulation of the AB region of
1
are summarized in Scheme 1. A general procedure for the the H NMR spectrum of 1 confirmed the observed eight-
synthesis of hydroxymethyl-functionalized phosphanes in- line pattern of higher order with partially overlapping sig-
volves hydrophosphanylation of the formyl group by ad- nals for the CH2 protons and their geminal coupling of JAB
2
dition of primary or secondary phosphanes to formalde- = 13 Hz and two different JP,H coupling constants of 5.4
hyde.[17] For the preparation of the title compound 1 we (P,A) and 3.9 Hz (P,B), respectively (Figure 1). Similar
used CyPH2[17] as starting material, which can easily be syn- coupling patterns were also observed for other bis(hydroxy-
thesized from commercially available and inexpensive chem- methyl) phosphanes like cam-P(CH2OH)2 (cam = 8-cam-
icals. The formylation reaction of CyPH2 with slight excess phanyl)[19] and FcP(CH2OH)2,[14] which exhibit bulky
of aqueous formaldehyde solution (36.5%) at room tem- groups directly bonded to the phosphorus atom.
perature produced the bis(hydroxymethyl)phosphane (1) in
As suggested previously[15] the close proximity of these
almost quantitative yield (Scheme 1). The isolation of com- bulky groups may cause restricted rotation around the P–
pound 1 can easily be achieved by removal of the solvent CH2 and/or CH2–O bonds. The ability of 1 to associate
and excess formaldehyde in vacuo. The latter synthesis via hydrogen bonds was confirmed by an X-ray diffraction
turned out to be much more efficient than the reported analysis, showing that the molecules constitute a two-di-
456
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 455–463

A Hydrophilic Phosphane Capable of Forming Hydrogen-Bonding Networks
FULL PAPER
1
Figure 1. H NMR-spectrum of 1; a) measured; b) simulated.[20]
mensional hydrogen bond network with the OH groups In basic aqueous solutions (NaOD/D2O), 2 is converted
serving as proton donors and acceptors (see next section). into the corresponding carboxylate with chemical equiva-
The apparently activated OH group of the hydroxymethyl- lent methylene protons for the NH–CH2–COO- moiety due
functionalized phosphane 1 can be used to synthesize vari- to fast inversion of configuration at the nitrogen atom on
ous new phosphorus ligands in biomedical applications. the NMR time scale. However, this does not affect the AB
Since phosphanyl-containing amino acids or peptides repre- pattern for the methylene protons of the P–CH2–N moiety.
sent new carrier ligands for the development of novel metal- The composition of 2 is proven by ESI mass spectrometry,
containing drugs, the synthesis of bio-compatible phospho- recorded in negative mode, showing the [M – H+]-ion peak
rus compounds is of increasing interest. A possible syn- at m/z = 289.3 as base-peak.
thetic route to such systems offers the Mannich-type con-
Oxidation of the phosphorus atom in 1 furnished the
densation of the OH groups in (hydroxymethyl)phosphanes new crystalline chalcogenides CyP(X)(CH2OH)2 (3) (X =
with the NH2 groups in amino acids and peptides, respec- O) and (4) (X = S). The phosphane oxide 3 results by
tively.[5] In fact, the Mannich-type condensation of CyP- controlled oxidation of 1 with one equimolar amount of
(CH2OH)2 with 3.5-fold excess of glycine in oxygen-free hydrogen peroxide in 81% yield (Scheme 1). The prepara-
water/ethanol at room temperature affords the phosphane- tion of the phosphane sulfide homolog 4 was achieved in
glycine conjugate CyP[CH2N(H)CH2COOH]2 (2), in which quantitative yield by stirring a solution of 1 in toluene
each hydroxymethyl group was reacted with one glycine with elemental sulfur at room temperature (Scheme 1).
molecule (Scheme 1). Addition of excess molar amounts of Both compounds are colorless crystalline solids, which are
glycine was necessary in order to prevent disubstitution re- soluble in water and protic organic solvents like alcohols,
actions at the nitrogen centers. The glycine-derived phos- but insoluble in apolar organic solvents in contrast to the
phane 2 was obtained as an air-stable, colorless crystalline parent phosphane 1. The chalcogenides 3 and 4 were
solid, which is moderately soluble in water, but insoluble in characterized by means of NMR spectroscopy and mass
organic solvents. Due to the expected protonation of the spectrometry. Their molecular structures were additionally
amino functions and deprotonation of the COOH groups, confirmed by single-crystal X-ray diffraction analyses (see
2 shows excellent solubility in aqueous Brønstedt acids and next section). As expected, the 31P NMR chemical shifts
bases. The new conjugate 2 was characterized by NMR of 3 (δ = 55.7 ppm) and 4 (δ = 54.5 ppm) are quite
spectroscopy and ESI mass spectrometry. Solutions of N- similar to values of related phosphane chalcogenides,[2,15]
1
protonated 2 in DCl/D2O show one 31P NMR resonance which usually appear at relatively low field. The H NMR
signal at δ = –24.4 ppm, similar to the values observed for spectra of both compounds show unresolved overlapping
related amino acid-functionalized phosphanes in acidic multiplets for the methylene protons of the PCH2OH
1
solutions.[5] The H NMR spectrum exhibits two different groups, which indicate the expected chemical inequiva-
sets of methylene protons: one for the methylene protons lence (AB part of an ABX spin system; A, B = 1H; X
of the P–CH2–N part and one for the NH2+–CH2–COOH
=
31P) of the latter. The 13C nucleus of the PCH2OH
moiety. The first represents the AB part of an ABX spin groups exhibits a doublet in the 13C{1H} NMR spectra of
1
2
system (A, B = H; X = 31P; JAB = 14.1, JP,A = 1.0 and 3 and 4, respectively, with characteristically large 1J(P,C)
2JP,B = 2.2 Hz), while the other is an AB spin system with- coupling constants (3: 75.6 Hz; 4: 66.7 Hz) for phosphane
out 31P coupling with a geminal A,B coupling of 17.2 Hz. chalcogenides.
Eur. J. Inorg. Chem. 2006, 455–463
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
457

M. Gonschorowsky, K. Merz, M. Driess
FULL PAPER
In order to probe the coordination ability of 1, the CD3OD shows one resonance signal at δ = –7.9 ppm for
monodentate phosphane ligand was allowed to react with the four chemically equivalent phosphorus atoms which is
Pt(+2) and Cu(+1) compounds, since such metal complexes broadened (h1/2 ca. 25 Hz) due to the presence of the
are of interest because of their important cytotoxic proper- 63/65Cu-quadrupole nuclei. Broadening of the resonance sig-
1
ties. In fact, the well established precursor Pt(COD)Cl2 re- nals is also observed in the H NMR spectrum of 6 which
acts with 1 in the molar ratio of 1:2 in dichloromethane at limits stereochemical information. While ESI-MS investi-
25 °C, affording solely cis-[PtCl2{CyP(CH2OH)2}2] (5) gations of 6 were in contrast to 5 unsuccessful, FAB mass
which can be isolated in 82% yield (Scheme 1). Complex 5 spectromeric measurements revealed at least the fragment-
is an air-stable colorless crystalline solid, which is soluble ion [Cu{CyP(CH2OH)2}2]+ at m/z = 415.2 as the largest
in alcohols and moderate soluble in water. Its characteriza- fragment.
tions are based on multi-nuclear NMR spectroscopy, ESI-
mass spectrometry and combustion analysis. Especially di-
agnostic is the 195Pt{1H} NMR spectrum of 5, which shows X-ray Crystal Structure Determinations
one triplet at δ = –4523 ppm according to the coupling of
Crystal structure elucidations were performed for the
the platinum nucleus with two chemically equivalent phos-
compounds 1, 3, 4 and 6. Because hydroxymethyl-function-
1
phorus atoms. The resulting JPt,P coupling constant of
alized phosphorus compounds represent oligoalcohol mole-
3490 Hz clearly indicates that the platinum atom has the
cules, they have a large tendency to associate via hydrogen
cis-configuration.[21] This is evident by the fact that the corre-
sponding trans-isomers of similar Pt complexes exhibit JPt,P
coupling constants which are around 1000 Hz lower than
bonding which makes them to versatile building blocks for
the construction of new architectures by molecular recogni-
tion for crystal engineering. In fact, the compounds show a
different variety of hydrogen bonding networks. Single crys-
1
the values for cis complexes (e.g., cis-[Pt{P(CH2OH)3}2I2]:
1JPt,P = 3227 Hz vs. trans-[Pt{P(CH2OH)3}2I2]: JPt,P
=
1
tals of 1 suitable for an X-ray diffraction analysis were
grown in EtOH/nBu2O. (Table 1). However, the hydrogen-
bonding network of 1 could not be analyzed by X-ray dif-
fraction studies due to the moderate crystal quality. The
compound crystallizes monoclinic with two independent
molecules 1A and 1B in the unit cell (Figure 2). Their
atomic distances and angles are practically identical and re-
semble the respective values observed for the related bis(hy-
droxymethyl) phosphanes (Fc-P(CH2OH)2,[15] FcCH2P-
2162 Hz).[21] This trend can be simplified explained by the
higher trans-influence of phosphorus compared to halide
ligands, which weakens a Pt–P bond and hence lowers the
Pt,P coupling constant. The 31P NMR spectrum of complex
5 in CD3OD shows one resonance signal at δ = 15.8 ppm
for the two equivalent phosphorus nuclei. Additionally,
1
195Pt-satellites can be observed, with the identical JPt,P
coupling constant as already observed in the corresponding
195Pt NMR spectrum. In the 13C{1H} NMR spectrum of
complex 5 two unresolved multiplets were observed at δ =
36.0 ppm and δ = 54.8 ppm. Due to potential coupling with
the adjacent phosphorus and platinum nuclei these signals
are assigned to the carbon atoms, which are directly bonded
to the phosphorus (C1–Cy and CH2OH). As expected and
similar to the “free” ligand 1 and its chalcogenides 3 and
4, the methylene protons of the PCH2OH groups of the
[2]
[13]
(CH2OH)2 or (HOCH2)2P–CH2CH2–P(CH2OH)2
.
Table 1. Selected bond lengths [Å] and angles [°] for CyP-
(CH2OH)2 (1).
Molecule 1A
Molecule 1B
lengths [Å]
P(1)–C(7)
P(1)–C(15)
P(1)–C(13)
C(7)–O(4)
C(15)–O(3)
angles [°]
1.879(1)
1.778(9)
1.778(6)
1.355(9)
1.389(4)
P(2)–C(14)
P(2)–C(12)
P(2)–C(3)
C(14)–O(1)
C(12)–O(2)
1.896(9)
1.790(9)
1.770(5)
1.362(1)
1.333(2)
1
complex 5 are chemically inequivalent. Thus, the H NMR
spectrum of 5 exhibits two broad multiplets at δ = 4.43 and
4.67 ppm for the inequivalent CH2 protons, showing gemi-
3
nal coupling of 14 Hz and JPt,H coupling constants of
18.6 Hz and 29.4 Hz, respectively, for the respective 195Pt-
C(7)–P(1)–C(15) 98.3(6)
C(14)–P(2)–C(12)
C(14)–P(2)–C(3)
C(12)–P(2)–C(3)
P(2)–C(14)–O(1)
P(2)–C(12)–O(2)
98.0(6)
satellites. The ESI mass spectra show the characteristic peak C(7)–P(1)–C(13) 102.2(6)
104.8(6)
101.9(6)
113.0(9)
113.2(8)
for the [M – Cl]+ ion at m/z = 583.8 in positive mode and
C(15)–P(1)–C(13) 101.1(6)
P(1)–C(7)–O(4)
P(1)–C(15)–O(3) 110.3(8)
116.0(9)
one for the [M + Cl]– ion peak at m/z = 653.8 in negative
mode, which are typical for related platinum chloride com-
plexes (e.g. cis-[PtCl2{P(FcCH2)(CH2OH)2}2]).[15]
O(1)···O(3)
O(3)···O(4)
O(4)···O(2)
2.620
2.584
2.651
Similar reaction of CyP(CH2OH), ligand 1 with CuI in
molar ratio of 1:2 in dichloromethane at room temperature
(Scheme 1) furnished air-stable, colorless crystals of 6,
In contrast to the limited geometrical analysis of 1, the
which are soluble in alcohols and moderate soluble in water. crystal structure determinations of the phosphane deriva-
According to an X-ray structure analysis, compound 6 tives CyP(O)(CH2OH)2 3 and CyP(S)(CH2OH)2 4 afforded
forms a dimer with two iodo-bridges between the Cu atoms better data sets (see Table 5) suitable for a topological
and the dimers are associated via hydrogen bonds in a dif- analysis of the hydrogen-bonding networks. The latter re-
ferent motif than 1, 3 and 4 (see next section). Complex 6 vealed other types of hydrogen-bonding networks than that
was also characterized by NMR spectroscopy, mass spec- of the related ferrocenyl-substituted compounds [FcP(X)-
trometry and elemental analysis. Its 31P NMR spectrum in (CH2OH)2 (X = O, S),[15] FcCH2P(S)(CH2OH)2,[2] and
458
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 455–463

A Hydrophilic Phosphane Capable of Forming Hydrogen-Bonding Networks
FULL PAPER
Figure 3. Molecular structure of CyP(O)(CH2OH)2 (3).
Table 2. Selected bond lengths [Å] and angles [°] for CyP(O)-
(CH2OH)2 (3).
P(1)–C(8)
P(1)–C(7)
P(1)–C(1)
P(1)–O(1)
C(8)–O(3)
C(7)–O(2)
O(3)–H(1)
O(2)–H(2)
H(1)···O(1A) 2.01(6)
H(2)···O(1A) 2.02(5)
O(3)···O(1A) 2.717(6)
O(2)···O(1A) 2.709(6)
1.808(6)
1.800(6)
1.795(6)
1.512(4)
1.422(6)
1.435(6)
0.71(5)
C(8)–P(1)–C(7)
C(8)–P(1)–C(1)
C(7)–P(1)–C(1)
C(8)–P(1)–O(1)
C(7)–P(1)–O(1)
C(1)–P(1)–O(1)
P(1)–C(8)–O(3)
P(1)–C(7)–O(2)
C(8)–O(3)–H(1)
C(7)–O(2)–H(2)
O(3)–H(1)···O(1A)
O(2)–H(2)···O(1A)
107.9(3)
107.2(3)
107.7(3)
109.8(2)
109.4(2)
114.6(2)
114.0(4)
113.4(4)
108(5)
Figure 2. Molecular structure (without hydrogen atoms) of the two
independent molecules of CyP(CH2OH)2 1 in the unit cell.
FcCH(CH3)P(CH2OH)2[16]] and presumably that of 1. The
molecular structures of compounds 3 and 4 are shown in
the Figure 3 and Figure 6, respectively, while selected bond
lengths and angles are given in the Table 2 and Table 3,
respectively. The P–O bond length of 1.512 (4) Å in 3 is
identical with that in FcP(O)(CH2OH)2 [1.510 (1) Å],[15]
which represents the hitherto only known structure for this
class of compounds. (Hydroxymethyl)phosphane oxides ex-
0.77(5)
90(4)
171(6)
149(5)
hibit P=O groups which are favorable hydrogen-bond ac- Table 3. Selected bond lengths [Å] and angles [°] for CyP-
(S)(CH2OH)2 (4).
ceptors and therefore are predestined to form hydrogen
bonds with proton donors like hydroxy groups. The hydro-
gen-bonding arrangement of compound 3 is shown in Fig-
ure 4, while Figure 5 depicts the crystal packing. In 3 each
P=O group forms bifurcated hydrogen bonding interactions
to the O–H groups of one neighboring molecule, with dis-
tances between hydrogen bonded oxygen atoms of 2.717
(6) Å for O(3)···O(1A) and 2.709 (6) Å for O(2)···O(1A),
respectively. This leads to an arrangement of linked mole-
cules via P=O···HO hydrogen bonds, where each molecule
has solely two connected neighbors. As it is shown in the
crystal packing of 3 (Figure 5), the one-dimensional chains
are not linked to each other. The P=O···HO motif was also
observed for the related compound FcP(O)(CH2OH)2.[15]
but in contrast to 3, FcP(O)(CH2OH)2 possesses a hydro-
gen-bonding network between three neighboring molecules,
where each P=O unit forms hydrogen bonds to OH groups
of different adjacent molecules.
P(1)–C(7)
P(1)–C(8)
P(1)–C(1)
P(1)–S(1)
C(7)–O(2)
C(8)–O(1)
O(2)–H(2)
O(1)–H(1)
H(1)···O(2)
H(2)···O(1)
O(1)···O(2)
O(2)···O(1)
1.828(2)
1.833(2)
1.815(2)
1.954(8)
1.419(2)
1.415(3)
0.72(3)
0.77(2)
1.94(2)
1.98(3)
2.686(2)
2.679(2)
C(7)–P(1)–C(8)
C(7)–P(1)–C(1)
C(8)–P(1)–C(1)
C(7)–P(1)–S(1)
C(8)–P(1)–S(1)
C(1)–P(1)–S(1)
P(1)–C(7)–O(2)
P(1)–C(8)–O(1)
C(7)–O(2)–H(2)
C(8)–O(1)–H(1)
O(1)–H(1)···O(2)
O(2)–H(2)···O(1)
103.6(1)
106.02(9)
104.27(9)
111.33(7)
113.84(7)
116.56(7)
112.5(1)
110.9(1)
112(2)
109.(3)
164(3)
168(3)
As expected, the distances and angles around the P atom
in the phosphane sulfide 4 (Table 3) are identical with that
of the related compound FcP(S)(CH2OH)2.[7] The structure
of 4 (Figures 6 and 7) shows a completely different hydro-
gen-bonding pattern compared to that of the oxide 3. The
hydrogen-bonding network and crystal packing of the sul-
Figure 4. Intermolecular hydrogen bonds between 3 in the crystal.
fide 4 are presented in Figure 7 and Figure 8, respectively. leads to the formation of a two-dimensional hydrogen
Interestingly and in contrast to the oxygen atom in 3, the bonding network between three adjacent molecules, in
sulfur atom in 4 is not involved in hydrogen-bonding. Hy- which each molecule is crosslinked to four neighboring
drogen bonds are formed exclusively between the hydroxy molecules.
groups, with each OH functionality acting as a donor in
Remarkably, the network of 4 with hydrogen bonded ten-
one and as an acceptor in another hydrogen bond. This membered rings is practically identical with that observed
Eur. J. Inorg. Chem. 2006, 455–463
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
459

M. Gonschorowsky, K. Merz, M. Driess
FULL PAPER
pattern with hydrogen bonds formed between the sulfur
atom and hydroxy groups as well as between OH groups.
The formation of O–H···S hydrogen bonds in
FcCH2P(S)(CH2OH)2 and FcCH(CH3)P(CH2OH)2 on the
one hand and the lack of O–H···S interactions in
FcP(S)(CH2OH)2 and 4 on the other hand is rather pecu-
liar. As already suggested previously,[15] the proximity of the
bulky groups to the phosphorus centers in FcP(S)-
(CH2OH)2 and 4 may effectively shield the sulfur atoms and
prevent hydrogen bonding interactions of the P=S group.
Additionally, the sulfur atom of the P=S group is a much
weaker hydrogen-bond acceptor compared to the P=O
functionality.
As shown in the crystal packing diagrams of the com-
pounds 3 (Figure 5) and 4 (Figure 8), the hydrophobic cy-
clohexyl groups have also an important influence on the
aggregation behaviour of the molecules. Due to van der
Waals interactions, the cyclohexyl groups are effectively
stacked on each other, which leads to the formation of alter-
nating hydrophobic and hydrophilic regions in the crystal
packing.
Figure 5. Crystal packing of CyP(O)(CH2OH)2 (3).
The structural elucidation of the copper complex 6 re-
vealed another new type of hydrogen-bonding network. The
molecular structure and the hydrogen-bonding pattern of
complex 6 are represented in the Figure 9 and Figure 10,
respectively, while selected distances and angles are given
in Table 4. The centrosymmetric complex 6 is a dimer and
possesses two iodo-bridges in a planar Cu2I2 ring. There
are other CuI–phosphane complexes known, having a four-
membered Cu2I2 core and terminal coordinated mono-
dentate phoshane ligands (e.g. [CuI(PPh2Me)2]2·SO2,[22]
[CuI(PH2Ph)2]2[23] and [CuI(PMe3)2]2[24]). Complex 6 repre-
sents the first example of a Cu(+1) complex containing
functionalized monodentate phosphane ligands coordi-
nated to a CuI dimer. The distances and angles of com-
pound 6 are unexceptional and similar to that of [Cu-
I(PMe3)2]2.[24]
Figure 6. Molecular structure of CyP(S)(CH2OH)2 (4).
Figure 7. Two-dimensional network of 4 via hydrogen bonds.
Figure 8. Crystal packing of CyP(S)(CH2OH)2 (4).
[15]
for the sulfur-free phosphane FcP(CH2OH)2
and remi-
niscent of that in the related sulfide FcP(S)(CH2OH)2.[15] In
contrast to 4, the hydrogen bonds in FcP(S)(CH2OH)2 are
formed between three neighboring molecules with a net-
work of alternating eight- and twelve-membered rings.
However, in contrast to the sulfide 4 and FcP(S)-
Figure 9. Molecular structure of [CuI{CyP(CH2OH)2}2]2 (6).
As expected, the crystal structure of 6 shows intermo-
(CH2OH)2, the structures of other related ferrocenyl-
[2]
derived
FcCH(CH3)P(CH2OH)2
compounds
FcCH2P(S)(CH2OH)2
and lecular hydrogen bonding interactions due to the presence
[16]
show
a
hydrogen-bonding of OH groups in the phosphane ligand. There exist two dif-
460
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 455–463

A Hydrophilic Phosphane Capable of Forming Hydrogen-Bonding Networks
FULL PAPER
two-dimensional networks, which are parallel stacked on
each other.
Conclusion
The amphiphilic cyclohexyl (hydroxymethyl)phosphane 1
is a valuable building block for designing novel hydrogen
bonding networks. Using the versatile reactivity of phos-
phane 1 a variety of functionalized phosphorus compounds
can be synthesized. Thus, Mannich-type condensation of 1
with glycine produced the air-stable amino acid function-
alized phosphane 2, and the crystalline derivatives 3 and 4
were prepared by simple oxidation reactions. The X-ray
crystal structure diffraction analyses revealed completely
different hydrogen bonding pattern for the oxide 3 and the
sulfide 4. While 3 shows intermolecular bifurcated hydrogen
bonding interactions between the strong P=O acceptor and
the O–H donor groups, the sulfur atom of 4 was not in-
volved in any hydrogen bond. The hydrogen bonding net-
work in 4 was exclusively formed by O–H···O–H interac-
tions and was similar to that observed for the related phos-
phane FcP(CH2OH)2.[14,15] In addition, the coordination
chemistry of 1 was studied which led to the air-stable
Figure 10. Hydrogen-bonding network in and crystal packing of
[CuI{CyP(CH2OH)2}2]2 (6).
complexes
cis-[PtCl2{CyP(CH2OH)2}2]
(5)
and
[CuI{CyP(CH2OH)2}2]2 (6), respectively. The crystal struc-
ture of the latter revealed another new type of hydrogen-
bonding network where one OH group of phosphane ligand
2 [with P(2)] is not involved in any hydrogen bond.
Table 4. Selected bond lengths [Å] and angles [°] of complex 6.
Cu(1)–I(1)
Cu(1)–IЈ(1)
Cu(1)–P(1)
Cu(1)–P(2)
P(1)–C(7)
P(1)–C(8)
P(1)–C(1)
P(2)–C(15)
P(2)–C(16)
P(2)–C(9)
C(7)–O(1)
C(8)–O(2)
C(15)–O(3)
C(16)–O(4)
2.716(4)
2.722(5)
2.258(4)
2.257(4)
1.839(7)
1.851(7)
1.851(7)
1.843(7)
1.830(7)
1.838(7)
1.416(8)
1.412(8)
1.439(7)
1.449(8)
Cu(1)–I(1)–CuЈ(1)
I(1)–Cu(1)–IЈ(1)
P(1)–Cu(1)–P(2)
P(1)–Cu(1)–I(1)
P(1)–Cu(1)–IЈ(1)
P(2)–Cu(1)–IЈ(1)
P(2)–Cu(1)–I(1)
Cu(1)–P(1)–C(7)
Cu(1)–P(1)–C(8)
Cu(1)–P(2)–C(15)
Cu(1)–P(2)–C(16)
P(1)–C(7)–O(1)
P(1)–C(8)–O(2)
P(2)–C(15)–O(3)
P(2)–C(16)–O(4)
O(1)–H(1)···O(4B)
78.5(1)
101.4(1)
123.45(7)
109.0(1)
105.70(7)
111.7(1)
103.3(1)
114.2(2)
115.0(2)
113.2(2)
112.2(2)
114.4(5)
112.7(4)
113.1(4)
114.0(4)
155.9(4)
Experimental Section
General Remarks: All manipulations were performed under dry and
oxygen-free argon. Solvents were dried according to standard
methods and saturated with argon or degassed, respectively. The
NMR spectra were recorded on a Bruker Avance DPX 250 MHz
spectrometer at room-temperature. Chemical shifts δ are given in
ppm and were referenced against Me4Si (1H, 13C; using residual
protonated solvent peak or the carbon resonance, respectively),
85% H3PO4 (31P) and H2PtCl6 in D2O (195Pt). ESI-mass spectro-
metric analysis were performed in the positive and the negative
mode using a Bruker Esquire 3000 instrument. The EI- and FAB-
mass spectra were recorded at a VG instruments Autospec/EBEE
spectrometer. Elemental analyses were carried out on a VarioEL
(CHN) elemental analyzer. CyPH2[25] and PtCl2(COD)[26] were pre-
pared according to published procedures. All other chemicals used
as starting materials were obtained commercially and without fur-
ther purification.
O(1)···O(4B) 2.702(8)
O(3A)···O(1) 2.684(8)
O(3A)–H(3A)···O(1) 164.2(4)
ferent types of intermolecular hydrogen bonds with the dis-
tances between the hydrogen bonded oxygen atoms O(1)···
O(4B) of 2.702(8) Å and O(3A)···O(1) of 2.684(8) Å, Preparation of CyP(CH2OH)2 (1): Aqueous formaldehyde (36.5%,
4.23 mL, 56.0 mmol) was placed in oxygen-free ethanol (10 mL)
and purged with argon at room temperature for 30 min. Then a
solution of CyPH2 (2.60 g, 22.4 mmol) in 10 mL of oxygen-free eth-
anol was added dropwise and the mixture was stirred overnight at
25 °C. After removal of the solvent in vacuo the residual colorless
solid is recrystallized from ethanol/di-n-butyl ether at –15 °C. Yield:
3.86 g, (98%). C8H17O2P (176.2): calcd. C 54.6, H 9.7; found C
54.4, H 10.1. 1H NMR (250.13 MHz, D2O): δ = 1.00–1.40 (m, 5
respectively (Figure 10). The hydroxy group O(1)–H(1) of
phosphane ligand 1 [with P(1)] acts as a donor in one hy-
drogen bond and as an acceptor in a second hydrogen bond
with two adjacent molecules 6. The hydroxy groups O(3)–
H(3) and O(4)–H(4) of phosphane ligand 2 [with P(2)] are
each involved in only one hydrogen bonding with two
neighboring molecules. At least each dimer molecule is as-
sociated via six hydrogen bonds with four adjacent mole-
cules, with the neighboring dimers are oriented about 90°
2
2
H, Cy), 1.44–1.98 (m, 6 H, Cy), 3.98 (dd, JP,H = 5.4, JH,H
13.0 Hz, 2 H, PCH2), 4.05 (dd, JP,H = 3.9, JH,H = 13.0 Hz, 2 H,
=
2
2
to the observed molecule. This leads to the formation of PCH2) ppm. 13C NMR (62.90 MHz, D2O): δ = 26.2 (s, C4-Cy),
Eur. J. Inorg. Chem. 2006, 455–463
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
461

M. Gonschorowsky, K. Merz, M. Driess
FULL PAPER
3
2
26.4 (d, JP,C = 10.6 Hz, C3-, C5-Cy), 29.2 (d, JP,C = 12.0 Hz, C2-, Preparation of CyP(S)(CH2OH)2 (4): Elemental sulfur (86 mg,
1
1
C6-Cy), 29.4 (d, JP,C = 13.8 Hz, C1-Cy), 57.3 (d, JP,C = 10.4 Hz,
PCH2) ppm. 31P NMR (101.25 MHz, D2O): δ = –11.4 (br. s) ppm.
EI-MS: m/z (%) = 176 [M+ (19)], 146 [M+ – CH2O (18)], 115
2.670 mmol) was added to a solution of phosphane 1 (470 mg,
2.670 mmol) in 10 mL toluene at room temperature. While stirring
for 30 min the sulfur disappeared and a colorless solid was formed.
After evaporation of the solvent the residue was re-dissolved in
ethanol (8 mL) and filtered. The solvent was again partly removed
in vacuo and diethyl ether was added causing the product to pre-
cipitate. The solid was filtered off and dried in vacuo yielding 4
as a colorless crystalline solid. Yield: 555 mg (100%). C8H17O2SP
(208.2): calcd. C 46.15, H 8.23; found C 45.9, H 8.15. 1H NMR
(250.13 MHz, D2O): δ = 1.10–1.81 (m, 11 H, Cy), 4.18 (m, 4 H,
PCH2) ppm. 13C NMR (62.90 MHz, D2O): δ = 25.1 (s, C-4 Cy),
+
+
[CyPH+ (17)], 83 [Cy+ (70)], 55 [C4H7 (100)] 41 [C3H5 (74)].
Preparation of CyP[CH2N(H)CH2COOH]2 (2): A solution of gly-
cine (0.83 g, 11.38 mmol) in degassed water (3.5 mL) was added via
a syringe to phosphane 1 (0.57 g, 3.24 mmol) in 1.5 mL oxygen-
free ethanol and stirred overnight at 25 °C. The formed solid was
filtered off and the filtrate evaporated giving the product as a color-
less crystalline solid. Yield: 808 mg (86%). 1H NMR (250.13 MHz,
DCl/D2O): δ = –0.92 to –0.80 (m, 5 H, Cy), –0.31 to –0.05 (m, 6
3
2
25.5 (d, JP,C = 3.8 Hz, C3-, C5-Cy), 26.5 (d, JP,C = 16.7 Hz, C-
2
2
H, Cy), 1.61 (br. d, JH,H = 14.1 Hz, 2 H, PCH2), 1.76 (dd, JP,H
1
1
2,C-6 Cy), 32.8 (d, JP,C = 52.3 Hz, C-1Cy), 58.1 (d, JP,C
=
= 2.2, 2JH,H = 14.1 Hz, 2 H, PCH2), 2.16 (d, 2JH,H = 17.2 Hz, 2 H,
66.7 Hz, PCH2) ppm. 31P NMR (101.25 MHz, D2O): δ = 54.5 (s)
ppm. EI-MS: m/z (%) = 208 [M+ (69)], 178 [M+-CH2O (9)], 127
[M+ – Cy + H (47)], 126 [M+ – Cy + 2 H (38)], 108 [M+ – Cy –
2
CH2COOH), 2.20 (d, JH,H = 17.2 Hz, 2 H, CH2COOH) ppm. 13
C
3
NMR (62.90 MHz, DCl/D2O): δ = 24.9 (s, C-4-Cy), 25.9 (d, JP,C
2
= 11.3 Hz C-3-, C-5-Cy), 27.8 (d, JP,C = 10.8 Hz, C-2-,C-6-Cy),
OH (100)], 83 [Cy+ (39)], 78 [HP(S)CH2 (84)], 55 [C4H7+ (82)], 41
+
1
1
32.8 (d, JP,C = 4.6 Hz, C-1-Cy), 43.6 (d, JP,C = 18.8 Hz, PCH2),
+
[C3H5 (70)].
3
48.4 (d, JP,C = 7.6 Hz, CH2COOH), 168.0 (s, COOH) ppm. 31P
NMR (101.25 MHz, DCl/D2O): δ = –24.4 (br. s) ppm. ESI-MS
Preparation of cis-[PtCl2{CyP(CH2OH)2}2] (5): Phosphane
1
(negative mode): 289.3 [M – H+].
(218 mg, 1.236 mmol) and Pt(COD)Cl2 (231 mg, 0.618 mmol) were
dissolved in CH2Cl2 (10 mL) and stirred for 2 h at room tempera-
ture. After standing for another 4 h at 25 °C the formed solid was
filtered off and dried in vacuo giving the product as a colorless
crystalline solid, which may be recrystallized from hot methanol.
Yield: 313 mg (82%). C16H34Cl2O4P2Pt (618.4): calcd. C 31.1, H
5.5; found C 31.2, H 5.8. 1H NMR (250.13 MHz, [D4]MeOH): δ =
1.21 –1.79 (m, 12 H, Cy-H3,–H4,–H5), 1.83 (br. m, 4 H, Cy-H2,-
Preparation of CyP(O)(CH2OH)2 (3): Aqueous hydrogen peroxide
(0.3%, 6 mL) was added to a solution of compound 1 (100 mg,
0.568 mmol) in 20 mL methanol and stirred in air for 10 min. The
solvent was removed at a rotor vapour, co-evaporated twice with
water (2×10 mL) and washed with dry ether (10 mL). After drying
in vacuo the product 3 was obtained as colorless crystalline solid.
Yield: 87 mg (81%). C8H17O3P (192.2): calcd. C 50.0, H 8.9; found
1
C 50.4, H 9.3. H NMR (250.13 MHz, D2O): δ = 1.10–1.41 (m, 4 H6), 2.21 (br. m, 4 H, Cy-H2,-H6), 2.58 (br. m, 2 H, Cy-H1), 4.43
2
2
3
H, Cy), 1.58 –1.85 (m, 6 H, Cy) 1.98 (m, 1 H, H1–Cy) 4.02 (m, 4 (m, JH,H = 14.0, JP,H = 0.8, JPt,H = 18.6 Hz, 4 H, PCH2), 4.67
4
2
2
3
H, PCH2) ppm. 13C NMR (62.90 MHz, D2O): δ = 24.4 (d, JP,C
=
(m, JH,H = 14.0, JP,H = 2.0, JPt,H = 29.4 Hz, 4 H, PCH2) ppm.
3
2
1 Hz, C-4-Cy), 25.7 (d, JP,C = 3.4 Hz, C3-, C-5-Cy), 25.9 (d, JP,C
13C NMR (62.90 MHz, [D4]MeOH): δ = 26.2 (br. s, C-4 Cy), 27.2/
1
3
= 12.7 Hz, C-2,C-6-Cy), 32.2 (d, JP,C = 61.8 Hz, C-1 Cy), 54.8 (d, 27.4 (d, JP,C = 6.0 Hz, C-3, C-5 Cy), 29.8 (br. s, C2-,C6-Cy), 36.0
1JP,C = 75.6 Hz, PCH2) ppm. 31P NMR (101.25 MHz, D2O): δ =
(m, C-1 Cy), 54.8 (m, PCH2) ppm. 31P NMR (101.25 MHz, [D4]-
1
55.7 (br. s) ppm. ESI-MS (negative mode): 191.3 [M – H+].
MeOH): δ = 15.8 [s; Pt-satellites (d), JPt,P = 3490 Hz] ppm.
Table 5. Crystallographic data for compounds 1, 3, 4 and 6.
1
3
4
6
Empirical formula
Formula mass
Crystal system
Space group
C8H17O2P
179.19
monoclinic
C2/c
C8H17O3P
192.19
monoclinic
P21/c
C8H17O2PS
208.25
monoclinic
P21/c
C8H17Cu2I2O8P4
1085.62
monoclinic
P21/n
Cell constants
a [Å]
b [Å]
c [Å]
34.28(2)
5.161(4)
22.210(5)
110.21(2)
3687(5)
6.613(3)
15.882(5)
6.4485(16)
11.102(3)
108.740(5)
1076.7(5)
4
9.48(2)
17.39(3)
13.99(2)
107.81(8)
2196(7)
31.132(16)
5.4195(19)
114.014(14)
1019.2(8)
β [°]
Volume [Å3]
Z
16
4
2
Density (calculated) [Mg·m–3]
Absorption coefficient [mm–1]
Crystal size [mm]
Theta range for data collection
Reflections collected
Independent reflections
Goodness-of-fit on F2
R indices [I Ͼ 2σ(I)]
1.269
0.251
0.3 x0.2×0.2
1.93 to 22.50
2644
1974 (Rint = 0.1165)
1.069
R1 = 0.1167,
wR2 = 0.2390
R1 = 0.2223,
wR2 = 0.2664
0.474/–0.448
1.252
0.239
0.3×0.2×0.1
2.62 to 25.01
3799
1486 (Rint = 0.0879)
1.033
R1 = 0.0790,
wR2 = 0.1874
R1 = 0.1250,
wR2 = 0.2142
0.443/–0.518
1.285
0.412
0.2×0.1×0.1
2.71 to 30.01
5351
2730 (Rint = 0.0309)
1.028
R1 = 0.0452,
wR2 = 0.1061
R1 = 0.0672,
wR2 = 0.1140
0.438/–0.305
1.642
2.562
0.3×0.2×0.2
2.31 to 25.07
7412
3572 (Rint = 0.0337)
1.028
R1 = 0.0468,
wR2 = 0.1194
R1 = 0.0616,
wR2 = 0.1302
2.456/–0.850
R indices (all data)
Largest diff. peak/hole [e·Å–3]
462
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 455–463

A Hydrophilic Phosphane Capable of Forming Hydrogen-Bonding Networks
FULL PAPER
1
195PtNMR (53.52 MHz, [D4]MeOH): δ = –4523 (t, JPt,P
=
[3] W. Vullo, Ind. Eng. Chem. Prod. Res. Dev. 1966, 5, 346.
[4] S. L. Vail, D. J. Daigle, A. W. Frank, Text. Res. J. 1982, 52,
3502 Hz) ppm. ESI-MS (positive mode): 583.8 [M – Cl]. ESI-MS
(negative mode): 653.8 [M + Cl].
738.
[5] D. E. Berning, K. V. Katti, C. L. Barnes, W. A. Volkert, J. Am.
Chem. Soc. 1999, 121, 1658.
[6] W. Henderson, H. H. Petach, G. M. Olsen, J. Chem. Soc.,
Chem. Commun. 1994, 2181.
[7] W. Henderson, G. M. Olsen, L. S. Bonnington, J. Chem. Soc.,
Chem. Commun. 1994, 1863.
[8] K. V. Katti, H. Gali, C. J. Smith, D. E. Berning, Acc. Chem.
Res. 1999, 32, 9.
[9] S. R. Gilbertson, X. W. Wang, J. Org. Chem. 1996, 61, 434.
[10] A. Fukuoka, W. Kosugi, F. Morishita, M. Hirano, L. McCaf-
frey, W. Henderson, S. Komiya, Chem. Commun. 1999, 489.
[11] C. W. Kohlpainter, W. A. Herrmann, Angew. Chem. 1993, 105,
1588.
[12] N. J. Goodwin, W. Henderson, Polyhedron 1998, 7, 4071.
[13] G. F. Nieckarz, T. J. R. Weakley, W. K. Miller, D. K. Lyon,
D. R. Tyler, Inorg. Chem. 1996, 35, 1721.
[14] S. R. Alley, W. Henderson, Inorg. Chem. Commun. 2001, 4, 741.
[15] W. Henderson, S. R. Alley, J. Organomet. Chem. 2002, 658,
181.
Preparation of [CuI{CyP(CH2OH)2}2]2 (6): A solution of phos-
phane 1 (107 mg, 0.61 mmol) in 3 mL of CH2Cl2 was added drop-
wise to a suspension of CuI (58 mg, 0. 305 mmol) in 3 mL of
CH2Cl2 at room temperature. After stirring for 4 h at 25 °C the
solvent was removed under reduced pressure and the solid re-dis-
solved in 2 mL hot degassed methanol. Colorless crystals of prod-
uct 6 were formed during 1 day standing at 25°, which were filtered
off and dried in vacuo. Yield: 152 mg (92%). C32H68Cu2I2O8P4
(1085.7): calcd. C 35.4, H 6.3; found C 34.9, H 6.0. 1H NMR
(250.13 MHz, [D4]MeOH): δ = 1.10–1.88 (m, 40 H, Cy), 2.01–2.20
(m, 4 H, 1-H Cy), 4.11 (br. s, 16 H, PCH2) ppm. 31P NMR
(101.25 MHz, [D4]MeOH): δ = –7.97 (br. s, w1/2 = 35 Hz) ppm.
+
FAB-MS: m/z (%) = 415.2 [Cu{CyP(CH2OH)2}2 (30)], 239.3 [Cu-
+
+
CyP(CH2OH)2 (24)], 176.2 [CyP(CH2OH)2 (34)].
X-ray Crystallographic Study: Crystals of 1, 3, 4 and 6 were
mounted on top of a thin glass fiber. Data were collected with a a
Bruker-AXS SMART1000 diffractometer with graphite-monochro-
mated Mo-Kα radiation (λ = 0.71073 Å). The crystal data are sum-
marized in Table 5. Structures were solved by direct methods
(SHELX-97) and refined (SHELXL-97) by full-matrix least-
squares methods. Except for 1, the positions of the O–H hydrogen
atoms were localized in the difference Fourier map and refined. All
other hydrogen atoms were introduced at calculated positions
(riding model), included in structure factor calculations,
and not refined. CCDC-260936 to -260938 (for 3, 4, 6) and
-283461 (for 1) contain the supplementary crystallographic
data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[16] T. V. V. Ramakrishna, A. J. Elias, A. Vij, J. Organomet. Chem.
2000, 602, 125.
[17] V. S. Reddy, K. V. Katti, C. L. Barnes, Inorg. Chim. Acta 1995,
240, 367.
[18] M. Grayson, US Patent US 3243450, 1966.
[19] R. A. Berrigan, D. K. Russell, W. Henderson, M. T. Leach,
B. K. Nicholson, G. Woodward, C. Harris, New J. Chem. 2001,
25, 322.
[20] J. C. Gómez, F. J. S. López, Programm: MestReC 3.69 1996–
20.
[21] J. W. Ellis, K. Harrison, P. A. T. Hoye, A. G. Orpen, P. G. Prin-
gle, M. B. Smith, Inorg. Chem. 1992, 31, 3026.
[22] P. G. Eller, G. J. Kubas, R. R. Ryan, Inorg. Chem. 1977, 16,
2454.
[23] R. J. Batchelor, T. Birchall, R. Faggiani, Can. J. Chem. 1985,
63, 928.
[1] a) H. Hellmann, J. Bader, H. Birkner, O. Schuhmacher, Justus
Liebigs Ann. Chem. 1962, 659, 49; b) N. J. Goodwin, W. Hen-
derson, B. K. Nicholson, Inorg. Chim. Acta 2002, 335, 113–
118.
[2] N. J. Goodwin, W. Henderson, B. K. Nicholson, J. K. Sarfo,
J. Fawcett, D. R. Russell, J. Chem. Soc., Dalton Trans. 1997,
4377.
[24] G. A. Bowmaker, R. D. Hart, B. E. Jones, B. W. Skelton, A. H.
White, J. Chem. Soc. Dalton Trans. 1995, 3063.
[25] R. Graf, Chem. Ber. 1952, 85, 9.
[26] J. X. McDermott, J. F. White, G. M. Whitesides, J. Am. Chem.
Soc. 1976, 98, 6521.
Received: September 15, 2005
Published Online: Decenber 1, 2005
Eur. J. Inorg. Chem. 2006, 455–463
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
463