Calcium-mediated hydrophosphorylation of organic isocyanates with diphenylphosphane oxide

Article abstract of DOI:10.1071/CH13259

The calcium-mediated addition of diphenylphosphane oxide to organic isocyanates and isothiocyanates yields N-alkyl and N-aryl substituted diphenylphosphorylformamides (E≤O, R≤iPr, tBu, cHex, Ph, C6H4-4-Br, C6H2-2,4,6-Me3, and Naph) and -thioformamides (E≤S, R≤iPr, cHex, Ph, and C6H4-4-Me), respectively, of the type Ph2P(O)-C(E)-N(H)R. All derivatives were characterized by IR and NMR spectroscopy as well as X-ray diffraction experiments. The wavenumbers of the N-H stretching modes are smaller for the thio analogues and N-aryl substituents. In the solid state all formamides and thioformamides form dimers by N-HO-P hydrogen bridges. The P-CCE bonds are significantly elongated compared with the P-CPh distances.

Full text of DOI:10.1071/CH13259

RESEARCH FRONT
CSIRO PUBLISHING
Aust. J. Chem. 2013, 66, 1264–1273
Full Paper
http://dx.doi.org/10.1071/CH13259
Calcium-mediated Hydrophosphorylation of Organic
Isocyanates with Diphenylphosphane Oxide
A
A
A
Stephan Harling, Julia Greiser, Tareq M. A. Al-Shboul,
¨
A
A
A B
,
Helmar Gorls, Sven Krieck, and Matthias Westerhausen
¨
A
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena,
Humboldtstrasse 8, D-07743 Jena, Germany.
B
Corresponding author. Email: m.we@uni-jena.de
The calcium-mediated addition of diphenylphosphane oxide to organic isocyanates and isothiocyanates yields N-alkyl and
t
c
N-aryl substituted diphenylphosphorylformamides (E ¼ O, R ¼ iPr, Bu, Hex, Ph, C6H4-4-Br, C6H2-2,4,6-Me3, and
Naph) and -thioformamides (E ¼ S, R ¼ iPr, cHex, Ph, and C6H4-4-Me), respectively, of the type Ph2P(O)–C(E)–N(H)R.
All derivatives were characterized by IR and NMR spectroscopy as well as X-ray diffraction experiments. The
wavenumbers of the N–H stretching modes are smaller for the thio analogues and N-aryl substituents. In the solid state
all formamides and thioformamides form dimers by N–H?O–P hydrogen bridges. The P–CCE bonds are significantly
elongated compared with the P–CPh distances.
Manuscript received: 17 May 2013.
Manuscript accepted: 1 July 2013.
Published online: 21 August 2013.
Introduction
Here we expand our investigations on calcium-mediated
hydrophosphanylation of organic isocyanates with diphenyl-
phosphane oxide, which do not react with each other in the
absence of a catalyst. This reaction attracted our special interest
because a calcium-triggered trimerization of cyclohexyl- and
phenylisocyanate was observed earlier.[15] However, addition of
HPPh2 to R–N¼C¼O succeeded with a lanthanum-basedcatalyst
in tetrahydrofuran (THF); the yields of Ph2P–C(O)–NHR were
between 38 (R ¼ adamantyl) and 88 % (R ¼ 4-F3C-C6H4).[16]
We reacted Ph2P(O)H instead of diphenylphosphane because
phosphane oxides readily form complexes with calcium ions
whereas phosphanes do not represent effective Lewis bases in
calcium-based chemistry.[9]
Lithium diphenylphosphanide reacts with equimolar
amounts of isocyanates yielding phosphorylformamides after
hydrolysis and treatment with dilute hydrogen peroxide.[17] In
another protocol, diarylphosphane oxide and diarylphosphane
sulfide reacted with isothiocyanates in the presence of catalytic
amounts of base (triethylamine) at 70–808C leading to the
formation of phosphorylformamides and phosphorylthio-
formamides, respectively.[18] In protic solvents (ethanol), tetra-
aryldiphosphanes reacted with phenylisothiocyanate to form
phosphanylthioformamides under P–P bond cleavage.[19]
Catalysis is a basic concept to reduce activation barriers of
chemical reactions and plays an important role in research and
industry. Most industrial products are produced by catalytic
processes. However, often these reactions rely on noble,
rare, and, hence, expensive metals such as late transition metals
and lanthanoids. Therefore, interest in other catalytically active
metals is growing in order to circumvent these challenges.
One of the most attractive candidates is calcium because this
alkaline earth metal is non-toxic regardless of its concentration
and is abundant worldwide, easily available, and inexpensive. In
addition, it combines the properties of typical s-block metals
(highly heteropolar bonds, salt-like compounds) and the early
transition metals (availability of 3d orbitals, catalytic activity,
Lewis-acidic character), as such, the research on calcium-based
catalysis has intensified within the past few years.[1,2]
In all catalytic processes calcium always maintains the
oxidation state of þ2, thereby excluding redox reactions.
Therefore, the catalytic cycle usually only contains addition
and substitution reactions as well as calciation steps. Typically,
there are two classes of calcium-mediated catalytic processes,
namely polymerization procedures (such as the polymerization
of lactide[3] or of styrene[4]) and heterofunctionalization
reactions (such as hydroamination[5–7] and hydrosilylation[8]).
In contrast to intensively investigated hydroamination as well as
lactide and styrene polymerization, the calcium-mediated hydro-
phosphanylation[1,2,9] of carbodiimides,[10,11] alkenes,[12] and
alkynes[12,13] plays a minor role. The calcium-mediated phos-
phanylation of substituted butadiynes with diphenylphosphane
yielded regio- and stereoisomers, depending on the substituent at
the butadiyne. If the same catalyst [(thf)4Ca(PPh2)2] is used
in the addition reaction of diphenylphosphane oxide with sub-
stituted butadiynes, different regioisomers were isolated.[14]
Results and Discussion
Synthesis
For the calcium-mediated addition of diphenylphosphane
oxide to organic isocyanates and isothiocyanates, a 0.1 M THF
solution of [(thf)4Ca(PPh2)2] was prepared.[20,21] A few
millilitres of this solution (5 mol-%) were added to a THF
solution of diphenylphosphane oxide. A slight excess of
organylisocyanates and -isothiocyanates was then added to this
Journal compilation Ó CSIRO 2013
www.publish.csiro.au/journals/ajc

Calcium-mediated Hydrophosphorylation
1265
H
O
O
P
N
E
R
cat.
PH
[(thf)4Ca(PPh2)2]
ꢀ R–N=C=E
E ꢁ O, S
R ꢁ alkyl, aryl
Scheme 1. Calcium-mediated synthesis of N-organyl-diphenylphosphorylformamides (E ¼ O) and
-thioformamides (E ¼ S).
calcium bis(diphenylphosphinite).[22] The phosphinite anion
adds to the carbon atom of R–N¼C¼E under formation of a
P–CCE bond yielding the intermediate [Ph2P(O)–C(E)–NR]ꢀ
anion. Protolysis by diphenylphosphane oxide finally leads to
the corresponding formamides and thioformamides under ref-
ormation of the catalyst [(thf)4Ca(OPPh2)2]. A catalytic cycle is
depicted in Scheme 2 taking into account that the first reaction
step is the formation of the catalytic species [(thf)4Ca(OPPh2)2]
from the precatalyst [(thf)4Ca(PPh2)2]. After complete conver-
sion the 31P NMR spectrum shows the resonances of the product
as well as of HPPh2 and [(thf)4Ca(PPh2)2] (Fig. 1) verifying
(i) that calcium bis(diphenylphosphinite) is the catalytically
active species and (ii) that a quantitative conversion into the
formamides and thioformamides was achieved. The yields
given in the experimental part are lower due to the fact that
they refer to the isolated crystalline material after recrystalliza-
tion and are not optimized.
δ
90 80 70 60 50 40 30 20 10
0 ꢂ10 ꢂ20 ꢂ30 ꢂ40
NMR Spectroscopy
Selected NMR and IR spectroscopic data of N-substituted
diphenylphosphorylformamides (E ¼ O, carbamoylphosphane
oxides) and -thioformamides (E ¼ S, thiocarbamoylphosphane
oxides) are summarized in Table 1. The thioformamides show
low field shifted resonances compared with the formamides.
Contrary to the more electronegative nature of oxygen, the
phosphorylformamides resonate upfield (,6 ppm in 31P) from
the respective phosphorylthioformamides. The heavier chalco-
δ
0 ꢂ10 ꢂ20 ꢂ30 ꢂ40
90 80 70 60 50 40 30 20 10
13
gen atom also leads to a strong low field shift of the
C
CE
signal
1
Fig. 1. 31P NMR spectrum of a [D8]THF solution of [(thf)4Ca(PPh2)2] (s, d
ꢀ16.4) with four equivalents of HP(O)Ph2 (d, d 17.4, 1JPH 481.5) leading to
an equilibrium with [(thf)4Ca(OPPh2)2] (s, d 80.3) and HPPh2 (d, d ꢀ40.9,
1JPH 215.4) (258C, 400 MHz) (top). On the bottom the 31P{1H} NMR
spectrum taken after complete conversion of tert-butyl isocyanate with HP
(O)Ph2 employing the catalyst [(thf)4Ca(PPh2)2] is depicted. Only the
resonances of N-tert-butyl-(diphenylphosphoryl)formamide (2) (d 9.5),
[(thf)4Ca(PPh2)2] (d ꢀ16.6), and HPPh2 (d ꢀ40.9) can be seen verifying
that [(thf)4Ca(OPPh2)2] is the catalytically active species.
(heavy atom effect). The J(P–CCO) coupling constants of the
formamides are ,30 Hz larger than those of the sulfur pendents.
Oxidation of the phosphorus atom results in a lower electronic
density and thus in an increased 1J(P–C) coupling constant. The
influence of the N-bound substituents on the NMR parameters
of the P–C–E fragments is much smaller than the variations
related to the chalcogen atom. Aryl groups cause a slight low
field shift of the 31P and slight high field shift of the
13
C
CE
resonances. Much more significant is the chemical shift dif-
ference of the N-bound hydrogen atom; for the aryl-
substituted derivatives the d(1HN) values are shifted by ,2 ppm
towards the lower field compared with alkyl-substituted
formamides. Furthermore, the deshielding of these H atoms
increases for the thioformamides.
The stretching frequencies of the C¼O and C¼S moieties
differ by ,130 cmꢀ1 mainly due to the larger reduced mass
of the sulfur-containing derivative. The N–H valence bond
stretching vibrations depend on the substitution pattern with
smaller wavenumbers for the thio-analogues and for N-aryl-
substituted derivatives. The IR parameters clearly confirm the
absence of an amide (A) iminol (B) tautomerism (E¼ O) or
thioamide (A) iminothiol (B) tautomerism (E¼ S). In the solid
state this isomer is stabilized by dimer formation by N–H?OPO
reaction mixture. The rate of conversion was monitored by
31P NMR spectroscopy. After complete conversion of
HP(O)Ph2 according to Scheme 1, all volatiles were removed
under vacuum and the solid residue was extracted with dichloro-
methane. Recrystallization from methanol or purification by
column chromatography gave analytically pure products.
A
31P NMR study of an equimolar mixture of [(thf)4Ca
(PPh2)2] and HP(O)Ph2 in THF showed an equilibrium between
these starting materials and the resulting [(thf)4Ca(OPPh2)2] and
HPPh2. Fig. 1 shows the NMR spectrum with the resonances of
all compounds allowing the determination of the equilibrium
constant K ¼ 0.013. The large excess of diphenylphosphane
oxide shifts the equilibrium towards the already well known

1266
S. Ha¨rling et al.
O
[(thf)4Ca(PPh2)2] ꢀ 2 HPPh2
H
O
P
N
E
R
2 HPPh2
ꢀ
[(thf)4Ca(OPPh2)2]
2 R–N=C=E
E ꢁ O, S
R ꢁ alkyl, aryl
O
R
2 HPPh2
E
N
(thf)x Ca
O
P
2
Scheme 2. Catalytic cycle for the synthesis of N-alkyl and N-aryl substituted diphenylphosphorylformamides (E ¼ O,
R ¼ iPr, tBu, cHex, Ph, C6H4-4-Br, C6H2-2,4,6-Me3, and Naph) and -thioformamides (E ¼ S, R ¼ iPr, cHex, Ph, and C6H4-4-
Me) using [(thf)4Ca(PPh2)2] as a precatalyst. Metalation of diphenylphosphane oxide yields catalytically active [(thf)4Ca
(OPPh2)2] which adds to R–N¼C¼E yielding an unobserved intermediate. Reaction with diphenylphosphane oxide gives the
products and reforms the calcium-based catalyst.
Table 1. Selected NMR and IR spectroscopic data for N-substituted diphenylphosphorylformamides (E 5 O)
and -thioformamides (E 5 S)
E
R
d(31P{1H})
d(13C¼E)
d(1HN)
1J(P–CCE) [Hz]
n(N–H) [cmꢀ1
]
n(C¼E) [cmꢀ1
]
A
O
iPr
14.8
14.5
14.9
15.6
15.8
16.2
16.2
20.6
20.7
21.6
21.5
168.7
168.9
168.7
168.1
168.3
168.5
168.5
195.4
195.2
194.1
193.3
120.7
119.6
120.7
122.8
122.3
121.2
122.4
87.4
3273
3201
3190
3178
3202
3125
3132
3138
3107
3076
3060
1641
1643
1643
1643
1645
1651
1651
1510
1510
1517
1523
tBu
7.42
7.51
cHex
Ph
9.68
C6H4-4-Br
Mes
9.51
9.11
Naph
iPr
cHex
10.12
9.44
S
9.48
88.9
Ph
11.20
11.15
89.6
C6H4-4-Me
90.0
AOverlapping with phenyl signals.
hydrogen bridges. In both cases the amide (A) and thioamide
derivatives (A, Scheme 3) are present in the solid state which is in
agreement with the NMR experiments of dissolved compounds.
small bond length of 148.81(11) pm in accordance with the
expectation for a strong P–O bond. This finding can be explained
by hyperconjugation from the negatively charged oxygen atom
into antibonding s*(P–C) orbitals, avoiding d-orbital participa-
tion at phosphorus (for a detailed discussion see Gilheany[23]), in
addition to electrostatic attraction. Similar findings were also
published for triphenylphosphane oxide which crystallized as
an orthorhombic (Pbca, P–O 149.1, av. P–C 180.3 p.m., av.
O–P–C 112.48)[24,25] and a monoclinic polymorph (P21/c, P–O
149.4, av. P–C 180.0 p.m., av. O–P–C 112.48).[25,26]
Molecular Structures
For comparison reasons the crystal structure of starting
diphenylphosphane oxide was determined. The molecular
structure and numbering scheme are shown in Fig. 2. Due to the
fact that multiple bonds are more demanding than single bonds
according to the VSEPR concept, the O–P–C/H angles are
larger than the ideal tetrahedral bond angle whereas the other
C–P–C/H bond angles are smaller than 1098. For this molecule
two mesomeric forms can be drawn with the ionic description
being the more appropriate (Scheme 4). The P–O bond shows a
Diphenylphosphane oxide contains a rather negative oxygen
atom whereas the P-bound hydrogen atom does not show a
distinct acidic behaviour due to very similar electronegativity
values (Allred-Rochow electronegativities of P 2.06, H 2.20)

Calcium-mediated Hydrophosphorylation
1267
H
O
characteristic for covalent P–H bonds. Therefore, aggregation in
the solid state does not occur by P–H?O–P hydrogen bridges
but short contacts are observed between the oxygen atom and
phenyl hydrogen atoms in para- and ortho-positions. These
contacts lead to a framework as shown in Fig. 3.
O
P
N
E
R
N
R
P
EH
The N-substituted diphenylphosphorylformamides (E ¼ O)
and -thioformamides (E ¼ S) form dimers in the solid state by
two N–H?O–P hydrogen bridges leading to a conformation
with the N–H and P–O moieties being directed to the same
side of the molecules. Due to the fact that all structures
are very similar only selected examples are depicted. The
molecular structures and numbering schemes of N-4-
bromophenyl-diphenylphosphorylformamide and N-isopropyl-
diphenylphosphorylthioformamide are shown in Figs 4 and 5,
respectively. For N-mesityl-diphenylphosphorylformamide the
aggregation by hydrogen bridges is clarified in Fig. 6. This
dimerizationoccursregardlessoftheN-boundalkyl orarylgroup.
A (E ꢁ O, S)
B
Scheme 3. Representation of the amide iminol (E ¼ O) and thioamide
iminothiol (E ¼ S) tautomerism.
O1
C2
C12
C11
P1
C3
C1
C7
C10
C4
C6
C9
C8
C5
C8A
C6A
O1A
C1A
C7A
C2A
C5A
C4A
P1A
Fig. 2. Molecular structure and numbering scheme of diphenylphosphane
oxide. The ellipsoids represent a probability of 40 %, H atoms are drawn
with arbitrary radii. Selected bond lengths (pm): P1–O1 148.81(11), P1–C1
180.15(14), P1–C7 179.82(15), P1–H1 132.7(18); angles (deg.): O1–P1–C1
113.31(7), O1–P1–C7 113.20(7), O1–P1–H1 116.2(8), C1–P1–C7 108.40
(7), C1–P1–H1 101.6(7), C7–P1–H1 102.9(8).
N1A
Br1A
C14A
C3A
O2A
O ꢂ
O
Fig. 4. Molecular structure and numbering scheme of N-(4-bromophenyl)-
1-(diphenylphosphoryl)formamide (5). The asymmetric unit contains two
crystallographically independent molecules which are distinguished by the
letters ‘A’ and ‘B’; due to very similar structures only molecule A is
depicted. The ellipsoids represent a probability of 40 %, H atoms are shown
with arbitrary radii.
Ph2P
ꢀ
Ph2P
H
H
Scheme 4. Representation of the mesomeric forms of diphenylphosphane
oxide.
O1B
S1
O1A
C3
P1A
P1B
C11
N1
C2
H6B
C1
P1
O1
H4A
C5
O1
P1
C4
C1
H6
C7
H4
Fig. 3. Part of the framework of diphenylphosphane oxide in the solid
state. The aggregation occurs by contacts between the oxygen atoms and
hydrogen atoms in ortho- and para-positions of the phenyl groups. All atoms
are shown with arbitrary radii.
Fig. 5. Molecular structure and numbering scheme of N-isopropyl-
(diphenylphosphoryl)thioformamide (8). The ellipsoids represent a proba-
bility of 40 %, hydrogen atoms are drawn with arbitrary radii.

1268
S. Ha¨rling et al.
Selected bond lengths and angles of the N-substituteddiphenyl-
longer than the P–CCS values of the diphenylphosphorylthio-
formamides. On the one hand, the C–E distances resemble
values of slightly elongated double bonds and are significantly
smaller than C–E single bonds. On the other hand, the N–CCE
distances are only marginally smaller than single bonds.
The central CCE carbon atoms of the formamide unit are in
distorted trigonal planar environments. Due to electrostatic
reasons, the E–CCE–N bond angles are widened whereas the
P–CCE–N angles are narrowed.
phosphorylformamides (E ¼ O) and -thioformamides (E ¼ S)
are listed in Table 2. The diphenylphosphoryl fragment shows
structural parameters that are very similar to those of Ph2P(O)H
and Ph3PO as discussed earlier. Whereas the P–CPh bond lengths
lie in the expected range, the P–CCE bond to the formamide
fragment is significantly elongated caused by electrostatic
repulsion between positively polarized phosphorus and carbon
atoms as depicted in Scheme 5. The oxygen atom (E ¼ O) is
more electronegative than sulfur leading to an enhanced positive
charge on the carbon atom CCE and therefore, the P–CCO bond
lengths of the diphenylphosphorylformamides are ,2 pm
Conclusion
The calcium complex [(thf)4Ca(PPh2)2] was used as a catalyst
system in THF solution. Addition of diphenylphosphane oxide
to this solution gave an equilibrium between [(thf)4Ca(PPh2)2]
and HP(O)Ph2 on the one side and [(thf)4Ca(OPPh2)2] and
HPPh2 on the other with an equilibrium constant K ¼ 0.013.
Organyl isocyanates and thioisocyanates were added to this
solution yielding N-organyl-diphenylphosphorylformamides
and -thioformamides, respectively. The degree of conversion
was monitored by 31P NMR spectroscopy and after complete
reaction, the catalyst [(thf)4Ca(PPh2)2] and free phosphane
HPPh2 were observed in addition to the product, whereas
HP(O)Ph2 was consumed completely.
C2
These N-organyl-diphenylphosphorylformamides and
-thioformamides crystallize as dimers with N–H?O–P hydro-
gen bridges. The P–CCE bonds are significantly longer than
those to the phenyl groups. This fact is a consequence of
electrostatic repulsion between positively polarized phosphorus
and carbon atoms. The influence of the N-bound alkyl and aryl
groups on the bonding parameters is small. The carbon-bound
chalcogen atom E influences the P–CCE distance with a signifi-
cantly elongated bond for E ¼ O because the larger electroneg-
ativity of oxygen enhances the positive charge on the carbon
N1
P1A
H1N1
O1A
O2
O2A
C1
P1
N1A
O1
C11
C17
atom and hence the repulsion between P and CCE
.
H
O ꢂ
N
R
Ph2Pꢀ
ꢀ
E ꢂ
Fig. 6. Representative example of the dimerization by N–H?O–P hydro-
gen bridges (dashed line) shown for N-mesityl-(diphenylphosphoryl)-
formamide (6). All atoms are shown with arbitrary radii, carbon-bound
hydrogen atoms are neglected for clarity reasons.
Scheme 5. Illustration of the positively polarized P and CCE atoms leading
to an elongation of the P–CCE bond.
Table 2. Selected structural data (average values where appropriate, bond lengths [pm] and angle [deg.]) of N-substituted
diphenylphosphorylformamides (E 5 O) and -thioformamides (E 5 S) (comparison: HP(O)Ph2: P5O 148.8(1), av. P–CPh 180.0,
P-H 133(2) pm)
E
R
P¼O
av. P–CPh
P–CCE
C¼E
N–CCE
N–CR
P–CCE–N
P–CCE–E
N–CCE–E
O
iPr
149.29(9)
149.2(1)
148.7(1)
148.8(1)
149.2(2)
149.1(2)
148.2(1)
148.7(1)
149.1(1)
149.4(1)
149.2(1)
149.1(1)
148.9(1)
149.3(1)
179.8
180.4
179.6
180.0
180.5
180.1
180.6
179.6
179.8
179.8
179.5
179.8
180.6
179.9
186.4(1)
186.8(1)
186.5(2)
186.2(1)
186.1(3)
186.4(3)
186.7(2)
186.7(2)
186.6(2)
184.2(2)
184.3(2)
184.4(2)
184.9(2)
184.6(1)
123.2(2)
123.3(2)
123.2(2)
122.9(2)
122.5(4)
122.4(4)
122.3(2)
122.5(2)
122.6(2)
166.4(2)
166.3(2)
166.4(2)
165.9(2)
165.6(1)
132.8(2)
133.1(2)
133.0(2)
134.3(2)
134.9(4)
135.1(4)
134.1(2)
134.6(2)
134.6(2)
131.8(2)
132.3(2)
132.3(2)
133.3(2)
133.7(2)
147.1(2)
148.9(2)
146.3(2)
142.6(2)
142.6(4)
142.1(4)
144.3(2)
143.5(2)
143.0(2)
147.5(2)
147.0(2)
147.0(2)
143.0(2)
143.2(2)
113.25(9)
114.8(1)
113.7(1)
113.66(9)
115.1(2)
113.7(2)
113.9(1)
114.5(1)
114.2(1)
112.8(1)
112.0(1)
112.7(1)
112.6(1)
111.61(9)
120.88(9)
118.9(1)
120.8(1)
118.7(1)
118.6(2)
119.2(2)
120.3(1)
119.5(1)
119.0(1)
119.43(9)
120.2(1)
119.6(1)
118.72(9)
119.53(8)
125.9(1)
126.2(1)
125.5(2)
127.6(1)
126.2(3)
127.0(3)
125.8(2)
125.9(1)
126.8(1)
127.7(1)
127.8(1)
127.7(1)
128.7(1)
128.9(1)
tBu
cHex
Ph
C6H4-4-BrA
Mes
NaphA
S
iPr
cHexA
Ph
C6H4-4-Me
ATwo crystallographically independent molecules.

Calcium-mediated Hydrophosphorylation
1269
Experimental
1532s, 1437m, 1171s (PO), 1112m, 750s, 691s. m/z 302 (15 %,
[M þ 1]þ), 202 (100, [HP(O)Ph2]þ), 183 (15), 155 (65), 125
(20, [HP(O)Ph]þ), 77 (30, [C6H5]þ), 57 (15, [C4H9]þ), 47 (25),
41 (10). Anal. Calc. for C17H20NO2P, 301.32: C 67.76, H 6.69,
N 4.65. Found: C 67.63, H 6.79, N 4.68 %.
General Remarks
All manipulations were carried out under an argon or nitrogen
gas atmosphere using standard Schlenk techniques. Solvents
were dried according to common procedures and distilled under
argon or nitrogen. Deuterated solvents were dried with sodium,
degassed, distilled, and saturated with inert gas. Chemicals
were purchased from Aldrich. All organylisocyanates or -iso-
thiocyanates were distilled before use.
N-Cyclohexyl-(diphenylphosphoryl)formamide (3)
Scale: 2.3 mL (0.23 mmol) of catalyst solution, 0.92 g
(4.58 mmol) of Ph2P(O)H, 0.63 g (5.04 mmol) of cyclohexyl
isocyanate; reaction period: 24 h; recrystallization from meth-
anol, yield: 1.05 g (70 %) of colourless crystals of 3. mp 1698C.
dH (600 MHz, CDCl3) 7.90 (4H, m), 7.56 (2H, m), 7.51 (4H, s,
NH),7.49 (4H, m), 3.90 (1H, m, CH), 1.93 (2H, m), 1.74 (2H, m),
1.62 (1H, m), 1.35 (2H, m), 1.27 (2H, m), 1.18 (1H, m).
General Procedure
A solution of the catalyst (0.05 equiv.) (0.1 M solution of
[(thf)4Ca(PPh2)2] in THF) was slowly added to a solution of
diphenylphosphane oxide (1 equiv.) in 30 mL of anhydrous THF
(per gram of diphenylphosphane oxide) at room temperature.
After stirring for approximately 15 min at room temperature the
organylisocyanate or -isothiocyanate (1.1 equiv.), dissolved or
suspended in 15 mL of anhydrous THF (per mmol of hetero-
cumulene), was added dropwise. The conversion of the sub-
strates was monitored with 31P NMR experiments at the
resonance of diphenylphosphane oxide after 12, 24, and 48 h.
After complete consumption of Ph2P(O)H, the solvent was
removed and the residual solid was extracted with 50 mL
of CH2Cl2. After removal of all volatiles under vacuum, the
crude product was purified by recrystallization or column
chromatography.
1
dC (151 MHz, CDCl3) 168.7 (d, JC–P 120.7, CO), 132.6
(d, JC–P 2.8, p-C), 131.8 (d, JC–P 9.7, m-C), 129.6 (d, JC–P
4
3
1
2
3
99.6, i-C), 128.8 (d, JC–P 12.2, o-C), 49.2 (d, JC–P 4.9,
CH-cHex), 32.9 (CH2-cHex), 25.4 (CH2-cHex), 24.9
(CH2-cHex). dP (162 MHz, CDCl3) 14.87. nmax (neat)/cmꢀ1
3191w (NH), 3024w, 2930m, 2850w, 1643s (CO), 1536s,
1438m, 1169s (PO), 1118s, 748s, 691s. m/z 328 (100 %,
[M þ 1]þ), 202 (100, [HP(O)Ph2]þ), 183 (20), 155 (80), 125
(40, [HP(O)Ph]þ), 83 (20, [C6H11]þ), 77 (70, [C6H5]þ), 55
(40, [C4H7]þ), 47 (50), 41 (30), 28 (10). Anal. Calc. for
C19H22NO2P, 327.36: C 69.71, H 6.77, N 4.28. Found: C 69.38,
H 6.67, N 4.32 %.
N-Phenyl-(diphenylphosphoryl)formamide (4)
Diphenylphosphane Oxide
Scale: 0.1 mL (0.5 mmol) of catalyst solution (5 M (thf)4Ca
(PPh2)2) in THF), 0.78 g (3.9 mmol) of Ph2P(O)H, 0.48 g
(4.02 mmol) of phenyl isocyanate; reaction period: 12 h; puri-
fication: column chromatography (silica; ethyl acetate/petro-
leum ether 5 : 1), yield: a few colourless crystals of 4. mp 1578C.
dH (600 MHz, CDCl3) 9.68 (1H, s, NH), 7.96 (4H, m), 7.71 (2H,
d, 3JH–H 8.6), 7.59 (2H, m), 7.50 (4H, m), 7.33 (2H, t, 3JH–H 8.0),
HP(O)PPh2 was synthesized according to literature proce-
dures.[27,28] Scale: 271 mL (27.1 mmol) of aqueous HCl (1 N)
and 0.56 g (2.77 mmol) of chlorodiphenylphosphane; purifica-
tion: recrystallization from a pentane–THF mixture; yield: 4.3 g
(94 %) of colourless crystals of HP(O)PPh2.
N-Isopropyl-(diphenylphosphoryl)formamide (1)
3
1
7.16 (1H, t, JH–H 7.3). dC (151 MHz, CDCl3) 168.1 (d, JC–P
122.8, CO), 136.9 (d, 3JC–P 9.5), 132.9 (d, 4J C–P 2.8, p-C), 131.9
Scale: 1.4 mL (0.14 mmol) of catalyst solution, 0.56 g
(2.77 mmol) of Ph2P(O)H, 0.26 g (3.05 mmol) of iso-
propylisocyanate; reaction period 24 h; purification: recrystal-
lization from methanol, yield: 0.51 g (61 %) of colourless
crystals of 1. mp 1478C. dH (400 MHz, CDCl3) 7.90 (4H,m),
7.51 (7H,m), 4.21 (1H, oct, CH), 1.15 (6H, d, CH3), 1.41 (9H, s).
3
2
(d, J
9.8, m-C), 129.2, 128.8 (d, J
12.4, o-C), 128.5,
C–P
C–P
125.6, 120.0. dP (162 MHz, CDCl3) 15.64. nmax (neat)/cmꢀ1
3178 (NH), 3047, 1643 (CO), 1597, 1535, 1497, 1435, 1312,
1242, 1173 (PO), 1111, 795, 748, 725, 694. m/z 322 (10 %,
[M þ 1]þ), 202 (100, [HP(O)Ph2]þ), 155 (10). Anal. Calc. for
C19H16NO2P, 321.31: C 71.02, H 5.02, N 4.36. Found: C 70.72,
H 5.26, N 4.36 %.
1
dC (101 MHz, CDCl3) 168.7 (d, JC–P 120.7, CO), 132.7
(d, JC–P 2.8, p-C), 131.7 (d, JC–P 9.6, m-C), 129.4 (d, JC–P
4
3
1
2
3
99.8, i-C), 128.8 (d, JC–P 12.2, o-C), 42.3 (d, JC–P 5.1, CH),
22.5 (CH3). dP (162 MHz, CDCl3) 14.84. nmax (neat)/cmꢀ1
3273w (NH), 2968w, 1641s (CO), 1524s, 1438m, 1173s (PO),
1147s, 748m, 692s. m/z 288 (10 %, [M þ 1]þ), 202 (100, [HP(O)
Ph2]þ), 201 (35, [P(O)Ph2]þ), 55 (40), 125 (15, [HP(O)Ph]þ),
77 (30, [C6H5]þ). Anal. Calc. for C16H18NO2P, 287.29: C 66.89,
H 6.32, N 4.88. Found: C 66.89, H 6.26, N 4.94 %.
N-(4-Bromophenyl)-(diphenylphosphoryl)formamide (5)
Scale: 1.2 mL (0.12 mmol) of catalyst solution, 0.5 g
(2.50 mmol) of Ph2P(O)H, 0.54 g (2.75 mmol) of 4-bromophenyl
isocyanate; reaction period: 48 h; recrystallization from
acetone, yield: 0.44 g (44 %) of colourless crystals of 5. Mp
2018C (dec.). dH (400 MHz, CDCl3) 9.51 (1H, s, NH), 7.94
(4H, m), 7.53 (10H, m). dC (151 MHz, CDCl3) 168.3 (d, 1JC–P
122.3, CO), 135.9 (d, 3JC–P 9.6), 132.9 (d, 4J C–P 2.6, p-C), 132.1,
N-tert-Butyl-(diphenylphosphoryl)formamide (2)
Scale: 0.8 mL (0.08 mmol) of catalyst solution, 0.32 g
(1.60 mmol) of Ph2P(O)H, 0.17 g (1.76 mmol) of tert-butyl
isocyanate; reaction period: 12 h; recrystallization from meth-
anol, yield: 0.34 g (74 %) of colourless crystals of 2. mp 1498C.
dH (400 MHz, CDCl3)7.88 (4H, m), 7.56 (2H, m), 7.47 (4H, m),
7.42 (1H, m, NH), 1.41 (9H, s). dC (101 MHz, CDCl3) 168.8
(d, 1JC–P 119.6, CO), 132.6 (d, 4JC–P 2.8, p-C), 131.7 (d, 3JC–P
9.6, m-C), 129.5 (d, 1JC–P 98.7, i-C), 128.7 (d, 2JC–P 12.2, o-C),
3
2
131.7 (d, J
9.8, m-C), 128.8 (d, J
12.4, o-C), 128.5
C–P
C–P
(d, 1JC–P 101.0, i-C), 121.4, 118.3. dP (162 MHz, CDCl3) 15.83.
nmax (neat)/cmꢀ1 3202w (NH), 3172w, 1645m (CO), 1592m,
1528m, 1486s, 1437m, 1394m, 1305m, 1237m, 1194s, 1169s
(PO), 1113s, 1073m (C–Br), 821s, 796m, 746m, 724s, 691s,
632s (C–Br). m/z 399 (10 %, [M]þ), 202 (100, [HP(O)Ph2]þ),
155 (20), 125 (10, [HP(O)Ph]þ), 77 (30, [C6H5]þ). Anal. Calc.
for C19H15BrNO2P, 400.21: C 57.02, H 3.68, N 3.38, Br 19.97.
Found: C 57.21, H 3.68, N 3.38, Br 19.74 %.
3
53.4 (d, JC–P 6.8, C-tBu), 28.7 (CH3). dP (162 MHz, CDCl3)
14.53. nmax (neat)/cmꢀ1 3201w (NH), 2974w, 1643s (CO),

1270
S. Ha¨rling et al.
N-Mesityl-(diphenylphosphoryl)formamide (6)
p-H), 7.47 (4H, m), 4.45 (1H, m, CH), 2.07 (2H, m), 1.77 (2H,
m), 1.66 (1H, m), 1.40 (2H, m), 1.26 (2H, m), 1.18 (1H, m). dC
(101 MHz, CDCl3) 195.1 (d, 1JC–P 88.9, CS), 132.8 (d, 3JC–P 9.4,
p-C), 132.6 (d, 4JC–P 2.8, m-C), 129.4 (d, 1JC–P 107.6, i-C), 128.4
Scale: 0.4 mL (2 mmol) of catalyst solution (5 M (thf)4Ca(P(O)
Ph2)2) in THF), 0.6 g (3.0 mmol) of Ph2P(O)H, 0.5 g (3.1 mmol)
of mesityl isocyanate; reaction period: 12 h; recrystallization
from THF, yield: 0.59 g (53 %) of colourless crystals of 7.
mp 1618C. dH (600 MHz, CDCl3) 9.11 (1H, s, NH), 7.97 (4H, t,
(d, JC–P 12.6, o-C), 54.1 (d, JC–P 4.8, CH-cHex), 31.2
(CH2-cHex), 25.4 (CH2-cHex), 24.6 (CH2-cHex). dP (162 MHz,
CDCl3) 20.65. nmax (neat)/cmꢀ1 3107w (NH), 2946m, 2855w,
1517s (CS), 1435m, 1384m, 1177s (PO), 1120s, 999s, 730s,
716s, 690s. m/z 344 (55 %, [M þ 1]þ), 343 (30, [M]þ), 202 (100,
[HP(O)Ph2]þ), 183 (10), 155 (55), 125 (30, [HP(O)Ph]þ),
98 (85, [HP(O)Ph]þ), 83 (10, [C6H11]þ), 77 (30, [C6H5]þ),
55 (20, [C4H7]þ), 47 (35), 41 (20), 28 (15). Anal. Calc. for
C19H22NOPS, 343.42: C 66.45, H 6.46, N 4.08, S 9.34. Found:
C 66.76, H 6.47, N 4.21, S 9.06 %.
2
3
3
3JH–H 9.0), 7.5 (2H, t, JH–H 7.2), 7.49 (4H, m), 6.70 (2H, s,
CH-Mes), 2.25 (3H, s, p-CH3-Mes), 1.74 (6H, s, o-CH3-Mes).
dC (151 MHz, CDCl3) 168.4 (d, 1JC–P 121.2, CO), 137.6, 134.8,
2
132.8, 131.8, 131.8, 129.1, 128.8 (d, JC–P 11.6, o-C), 21.0
(p-CH3-Mes), 18.4 (o-CH3-Mes). dP (162 MHz, CDCl3) 16.16.
nmax (neat)/cmꢀ1 3125 (NH), 2947, 1651 (CO), 1504, 1435,
1242, 1165 (PO), 1111, 1095, 748, 725, 694. m/z 364 (2 %,
[M þ 1]þ), 202 (100 %, [HP(O)Ph2]þ), 161 (76, [Mes-NCO]þ),
155 (32), 146 (60), 125 (12, [HP(O)Ph]þ), 91 (22, [C7H7]þ), 77
(35, [C6H5]þ). Anal. Calc. for C22H22NO2P, 363.39: C 72.71,
H 6.10, N 3.85. Found: C 71.90, H 6.43, N 3.74 %.
N-Phenyl-(diphenylphosphoryl)thioformamide (10)
Scale: 1.2 mL (0.12 mmol) of catalyst solution, 0.5 g (2.5 mmol)
of Ph2P(O)H, 0.37 g (2.75 mmol) of N-phenyl isothiocyanate;
reaction period: 48 h; recrystallization from methanol, yield:
0.48 g (57 %) of yellow crystals of 10. mp 1708C. dH (400 MHz,
CDCl3)11.22 (1H, s, NH), 8.09 (2H, d, 3JH–H 7.8), 8.01 (4H, m),
7.60 (2H, m), 7.49 (4H, m), 7.43 (2H, t, 3JH–H 7.9), 7.30 (1H, t,
3JH–H 7.4), 1.66 (1H, m), 1.40 (2H, m), 1.26 (2H, m), 1.18
(1H, m). dC (101 MHz, CDCl3) 194.1 (d, 1JC–P 89.6, CS), 138.5
(d, JC–P 11.5 Hz), 133.0 (d, 3JC–P 9.4, p-C), 132.8 (d, 4JC–P 2.9,
N-Naphthyl-(diphenylphosphoryl)formamide (7)
Scale: 0.5 mL (2.5 mmol) of catalyst solution (5 M [(thf)4Ca
(P(O)Ph2)2] in THF), 0.68 g (3.4 mmol) of Ph2P(O)H, 0.68 g
(4.0 mmol) of naphthyl isocyanate; reaction period: 12 h;
recrystallization from THF, yield: 0.99 g (79 %) of colourless
crystals of 7. mp 1568C. dH (400 MHz, CDCl3) 10.12 (1H, s,
NH), 8.20 (1H, d, 3JH–H 7.5), 8.02 (5H, m), 7.86 (1H, d, 3JH–H
9.0,), 7.72 (1H, d, 3JH–H 8.2), 7.60 (2H, m), 7.53 (6H, m), 7.46
(1H, t, J 7.9). dC (101 MHz, CDCl3) 168.4 (d, 1JC–P 122.4, CO),
134.0, 132.9 (d, 4JC–P 2.7, p-C), 131.9 (d, 3JC–P 9.7, m-C), 131.0
(d, 3J C–P 9.3, m-C), 128.9 (d, 2JC–P 12.4, o-C), 128.9 (d, 1JC–P
100.3, i-C), 128.8, 126.8, 126.8, 126.5, 126.4, 126.0, 125.6,
120.4, 119.3. dP (162 MHz, CDCl3) 16.2. nmax (neat)/cmꢀ1 3132
(NH), 2955, 1651 (CO), 1520, 1497, 1435, 1165 (PO), 1119,
1095, 795, 772, 748, 732, 694. m/z 372 (10 %, [M þ 1]þ), 371
(10, [M]þ), 202 (100, [HP(O)Ph2]þ), 169 (100, [Naph-NCO]þ),
155 (45), 140 (70, [Naph-N]þ), 124 (35, [P(O)Ph]þ), 114 (40),
77 (50, [C6H5]þ). Anal. Calc. for C23H18NO2P, 371.37: C 74.39,
H 4.89, N 3.77. Found: C 74.30, H 5.23, N 3.91 %.
1
2
m-C), 129.2, 129.0 (d, JC–P 108.2, i-C), 128.5 (d, JC–P 12.7,
o-C), 121.7. dP (162 MHz, CDCl3) 21.58. nmax (neat)/cmꢀ1
3076w (NH), 3019w, 2987w, 1594m, 1523m (CS), 1488m,
1479m, 1435s, 1368s, 1180s (PO), 1108s, 1092m, 1010s, 859m,
765m, 749m, 715s, 689s. m/z 338 (60 %, [M þ 1]þ), 337
(95, [M]þ), 202 (90, [HP(O)Ph2]þ), 183 (45), 155 (100), 135
(35, [Ph-NCS]þ), 125 (80, [HP(O)Ph]þ), 77 (90, [C6H5]þ), 47
(70). Anal. Calc. for C19H16NOPS, 337.38): C 67.64, H 4.78,
N 4.15, S 9.50. Found: C 68.04, H 4.73, N 4.20, S 9.37 %.
N-(p-Tolyl)-(diphenylphosphoryl)thioformamide (11)
Scale: 2.1 mL (0.21 mmol) of catalyst solution, 0.86 g
(4.25 mmol) of Ph2P(O)H, 0.7 g (4.7 mmol) of N-p-tolyl iso-
thiocyanate; reaction period: 12 h; recrystallization from THF,
yield: 0.63 g (42 %) of yellow crystals of 11. mp 1718C. dH
(400 MHz, CDCl3) 11.15 (1H, d, J 7.8, NH), 8.00 (6H, m), 7.59
(2H, m), 7.49 (4H, m), 7.212 (2H, m), 2.36 (3H, s, CH3 p-Tol).
N-Isopropyl-(diphenylphosphoryl)thioformamide (8)
Scale: 1.3 mL (0.13 mmol) of catalyst solution, 0.5 g
(2.50 mmol) of Ph2P(O)H, 0.28 g (2.77 mmol) of N-isopropyl
isothiocyanate; reaction period: 24 h; recrystallization from
methanol, yield: 0.38 g (50 %) of yellow crystals of 8. mp 1568C.
dH (400 MHz, CDCl3)9.44 (1H, s, NH), 7.96 (4H, m), 7.57 (2H,
m, p-H), 7.47 (4H, m), 4.73 (1H, m, CH), 1.34 (6H, d, 3JH–H 6.6).
dC (101 MHz, CDCl3) 195.4 (d, 1JC–P 87.4, CS), 132.8 (d, 3JC–P
9.4, m-C), 132.7 (d, 4JC–P 2.8, p-C), 129.3 (d, JC–P 107.7, i-C),
1
dC (101 MHz, CDCl3) 193.2 (d, JC–P 90.0, CS), 137.6 (p-C
p-Tol), 136.1 (d, 3JC–P 11.6, i-C p-Tol), 133.0 (d, 3JC–P 9.4, p-C),
132.8 (d, 4JC–P 2.8, p-C), 129.6, 129.2 (d, JC–P 104.3, i-C), 128.5
2
(d, JC–P 12.6, o-C), 121.7, 21.3 (CH3 pTol). dP (162 MHz,
CDCl3) 21.52. nmax (neat)/cmꢀ1 3060w (NH), 2941m, 2855w,
1509m (CS), 1433m, 1357m, 1167s (PO), 1117m, 1100m,
1015m, 819m, 750m, 725s, 689s. m/z 352 (55 %, [M þ 1]þ), 351
(75, [M]þ), 202 (100, [HP(O)Ph2]þ), 183 (30), 155 (90), 149
(20, [pTol-NCS]þ), 125 (50, [HP(O)Ph]þ), 91 (25, [C7H7]þ), 77
(30, [C6H5]þ), 47 (30). Anal. Calc. for C20H18NOPS, 351.40):
C 68.36, H 5.16, N 3.99, S 9.12. Found: C 68.78, H 4.73, N 4.20,
S 9.37 %.
2
3
128.4 (d, JC–P 12.6, o-C), 47.3 (d, JC–P 4.8, CH-iPr), 21.1
(CH3-iPr). dP (162 MHz, CDCl3) 20.60. nmax (neat)/cmꢀ1
3138m (NH), 2976w, 1510 (CS), 1455m, 1438s, 1384s, 1189s
(PO), 1171s, 1148m, 1132s, 1100s, 1002s, 842m, 829m, 750s,
726s, 712s, 688s, 589s. m/z 304 (20 %, [M þ 1]þ), 303 (70,
[M]þ), 202 (100, [HP(O)Ph2]þ), 155 (30), 125 (10, [HP(O)
Ph]þ), 77 (10, [C6H5]þ). Anal. Calc. for C16H18NOPS, 303.36:
C 63.35, H 5.98, N 4.62, S 10.57. Found: C 63.59, H 6.11,
N 4.63, S 10.54 %.
Structure Determinations
The intensity data for the compounds were collected on a Nonius
KappaCCD diffractometer using graphite-monochromated
MoKa radiation. Data were corrected for Lorentz and polariza-
tion effects but not for absorption effects.[29,30]
)
and refined by full-matrix least-squares techniques against
F2o (SHELXL-97[31]). The hydrogen atoms bound to the
N-Cyclohexyl-(diphenylphosphoryl)thioformamide (9)
Scale: 2.0 mL (0.2 mmol) of catalyst solution, 0.8 g (3.96 mmol)
of Ph2P(O)H, 0.61 g (4.35 mmol) of N-cyclohexyl isothiocya-
nate; reaction period: 48 h; recrystallization from methanol,
yield: 0.65 g (48 %) of yellow crystals of 9. mp 2008C. dH
(400 MHz, CDCl3) 9.48 (1H, s, NH), 7.96 (4H, m), 7.56 (2H, m,
The structures were solved by direct methods (SHELXS[31]

Calcium-mediated Hydrophosphorylation
1271
Table 3. Crystal data and refinement details for the X-ray structure determinations of the compounds Ph P(O)H and 1 5
]
2
Parameter
Ph2P(O)H
1
2
3
4
5
Formula
fw [g molꢀ1
T [8C]
C12H11OP
202.18
C16H18NO2P
287.28
C17H20NO2P
301.31
C19H22NO2P
327.35
C19H16NO2P
321.30
C19H15BrNO2P
400.20
]
ꢀ140(2)
Monoclinic
P21/n
ꢀ140(2)
Monoclinic
P21/n
ꢀ140(2)
Monoclinic
P21/n
ꢀ90(2)
Monoclinic
P21/n
ꢀ140(2)
Triclinic
P¯ı
ꢀ140(2)
Triclinic
P¯ı
Crystal system
Space group
˚
a [A]
˚
b [A]
˚
c [A]
8.4539(1)
13.5102(4)
9.1050(2)
90
8.3097(1)
20.1442(4)
9.6291(2)
90
8.5679(2)
10.6779(2)
17.1728(4)
90
11.0400(4)
11.4605(4)
14.4545(4)
90
8.6603(3)
8.7683(2)
11.3657(3)
109.126(2)
102.485(1)
94.979(2)
784.43(4)
2
10.1083(2)
11.2989(3)
17.5316(3)
73.282(1)
88.625(1)
64.483(1)
1719.04(6)
4
a [deg.]
b [deg.]
g [deg.]
103.257(1)
90
112.209(1)
90
93.636(1)
90
107.729(2)
90
3
˚
V [A ]
1012.20(4)
4
1492.26(5)
4
1567.93(6)
4
1741.98(10)
4
Z
r [g cmꢀ3
]
1.327
1.279
1.276
1.248
1.360
1.546
m [cmꢀ1
Measured data
]
2.32
1.85
1.79
1.67
1.84
24.95
6142
9619
9389
12 116
4874
10 933
Data with I . 2s(I)
2091
3114
3146
2751
3328
6717
Unique data (Rint
)
2313/0.0255
0.0869
3403/0.0222
0.0828
3562/0.0259
0.0917
3974/0.0527
0.1091
3546/0.0141
0.0875
7771/0.0240
0.0956
wR2 (all data, on F2)A
R1 (I . 2s(I))A
SB
0.0356
0.0330
0.0361
0.0426
0.0362
0.0445
1.055
1.055
1.058
1.015
1.029
1.113
ꢀ3
˚
Res. dens. [e A
]
0.338/ꢀ0.354
936826
0.380/ꢀ0.340
936827
0.386/ꢀ0.292
936828
0.250/ꢀ0.337
936828
0.407/ꢀ0.338
936830
0.468/ꢀ0.552
936831
CCDC No.
Formula
fw [g molꢀ1
C22H22NO2P
363.38
C23H18NO2P
371.35
C16H18NOPS 0.5 CH4O
319.37
C19H22NOPS
343.41
C19H16NOPS
337.36
C20H18NOPS
351.38
]
T [8C]
Crystal system
ꢀ90(2)
Monoclinic
P21/n
ꢀ140(2)
Monoclinic
P21/c
ꢀ140(2)
Monoclinic
C2/c
ꢀ140(2)
Monoclinic
P21/c
ꢀ140(2)
Triclinic
ꢀ140(2)
Monoclinic
P21/n
Space group
˚
a [A]
˚
b [A]
Pı
¯
11.7253(4)
8.4405(3)
20.1398(7)
90
15.6451(3)
11.2942(1)
21.9693(3)
90
13.3165(4)
15.5250(3)
16.2116(5)
90
13.9338(2)
18.1210(2)
15.1573(2)
90
8.5936(3)
8.7577(2)
12.0315(4)
101.854(2)
109.716(1)
94.235(2)
824.10(4)
2
12.3787(2)
10.7739(2)
13.8783(2)
90
˚
c [A]
a [deg.]
b [deg.]
g [deg.]
105.766(2)
90
107.800(1)
90
91.444(1)
90
109.217(1)
90
107.163(1)
90
3
˚
V [A ]
1918.20(12)
4
3696.12(9)
8
3350.50(16)
8
3613.88(8)
8
1768.48(5)
4
Z
r [g cmꢀ3
]
1.258
1.335
1.266
1.262
1.360
1.320
m [cmꢀ1
Measured data
Data with I . 2s(I)
Unique data (Rint
]
1.59
1.67
2.9
2.71
2.97
2.79
13 124
21 719
10 066
22 030
5227
10 662
3339
7319
3457
6894
3422
3712
)
4377/0.0441
0.1080
8458/0.0291
0.1020
3842/0.0254
0.0868
8271/0.0390
0.1007
3712/0.0177
0.0885
4030/0.0288
0.0870
wR2 (all data, on F2)A
R1 (I . 2s(I))A
SB
0.0430
0.0405
0.0369
0.0425
0.0378
0.0326
1.005
1.062
1.079
1.076
1.087
1.039
ꢀ3
˚
Res. dens. [e A
]
0.329/ꢀ0.327
936832
0.342/ꢀ0.347
936833
0.362/ꢀ0.311
936834
0.396/ꢀ0.310
936835
0.392/ꢀ0.287
936836
0.358/ꢀ0.293
936837
CCDC No.
ADefinition of the R indices: R1 ¼ (Sj|Fo| ꢀ |Fc|j)/S|Fo|; wR2 ¼ {S[w(Fo2 ꢀ Fc2)2]/S[w(F2o)2]}1/2 with wꢀ1 ¼ s2(F2o) þ (aP)2 þ bP; P ¼ [2Fc2 þ Max(F2o]/3.
BS ¼ {S[w(F2o ꢀ Fc2)2]/(No ꢀ Np)}1/2
.
amine-groups N1 of all compounds were located by difference
Fourier synthesis and refined isotropically. All other hydrogen
atoms were also refined isotropically with the exception of those
of compound 3 which were included at calculated positions with
fixed thermal parameters. All non-hydrogen atoms were refined
anisotropically.[31] Crystallographic data as well as structure
solution and refinement details are summarized in Table 3. XP
(SIEMENS Analytical X-ray Instruments, Inc.) was used for
structure representations.
supplementary publication CCDC-936826 for Ph2P(O)H,
CCDC-936827 for 1, CCDC-936828 for 2, CCDC-936829 for 3,
CCDC-936830 for 4, CCDC-936831 for 5, CCDC-936832 for 6,
CCDC-936833 for 7, CCDC-936834 for 8, CCDC-936835 for 9,
CCDC-936836 for 10, and CCDC-936837 for 11. Copies of the
data can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK [E- mail: deposit@ccdc.
cam.ac.uk].
Supplementary Material
Crystallographic Data
Crystallographic data (excluding structure factors) has been
deposited with the Cambridge Crystallographic Data Centre as
Molecular structures and numbering schemes of compounds
1–4, 6, 7, and 9–11 are available on the Journal’s website.

1272
S. Ha¨rling et al.
Acknowledgement
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The authors thank the German Research Foundation (DFG, Bonn/Germany)
and the Fonds der Chemischen Industrie (VCI/FCI, Frankfurt/Germany) for
financial support. They also acknowledge the support of Gritt Volland and
Katja Wimmer.
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