NCN chelated organoantimony(III) and organobismuth(III) phosphinates and phosphites: Synthesis, structure and reactivity

Article abstract of DOI:10.1002/ejic.201000746

The reaction of the organoantimony and organobismuthoxides [LSbO] ₂ (1) and [LBiO]₂ (2), where L = [2,6-(Me ₂NCH₂)₂C₆H₃] ^-, with phenylphosphinic acid in a 1:4 molar r

Full text of DOI:10.1002/ejic.201000746

FULL PAPER
DOI: 10.1002/ejic.201000746
NCN Chelated Organoantimony(III) and Organobismuth(III) Phosphinates
and Phosphites: Synthesis, Structure and Reactivity
[a]
[a]
[a]
[a]
[a]
ˇ
ˇ
˚ˇ ˇ
ˇ
ˇ
Tomás Svoboda, Roman Jambor, Ales Ruzicka, Zdenka Padelková, Milan Erben,
and Libor Dostál*[a]
Keywords: Antimony / Bismuth / Phosphorus / Chelates / X-ray diffraction
The reaction of the organoantimony and organobismuth
oxides [LSbO]2 (1) and [LBiO]2 (2), where [2,6-
While the organoantimony compounds 3, 5 and 7 are stable
in solution, the organobismuth congeners showed only lim-
ited stability in solution and underwent a redox process in-
volving to the reduction of the bismuth ions, and oxidation
of the phosphorus ions from the +III to +V oxidation state.
The reaction pathway associated with the redox process was
studied with the system bismuth oxide 2 + Ph2P(O)(H), which
gave compound LBi[OP(O)(Ph)2]2 (14) as a result of the oxi-
dation of the phosphorus ion. All compounds were charac-
terized by elemental analysis, 1H, 13C and 31P NMR spec-
troscopy and IR spectroscopy. The solid-state molecular
structures of compounds 3, 5a {LM[O2P(H)(O)][(HO)2P(H)-
(O)]} and 7 were determined by X-ray diffraction.
L
=
(Me2NCH2)2C6H3]–, with phenylphosphinic acid in a 1:4 mo-
lar ratio gave the molecular organoantimony and organobis-
muth phosphinates LM[OP(H)(O)(Ph)]2 [M = Sb (3), Bi (4)].
Similarly, the reaction of 1 and 2 with H3PO3 gave the sec-
ondary phosphites LM[OP(H)(O)(OH)]2 [M = Sb (5), Bi (6)] or
the fully deprotonated phosphite {LM[O2P(H)(O)]}2 [M = Sb
(7), Bi (8)] depending on whether the molar ratio of the start-
ing materials was 1:4 or 1:2. The syntheses of novel mixed
phosphinate-phosphite LSb[OP(H)(O)(OH)][OP(H)(O)(Ph)]
(9), phosphonate-phoshinate LSb[OP(tBu)(O)(OH)][OP(H)-
(O)(Ph)] (10) and phosphonate-phosphite LSb[OP(tBu)-
(O)(OH)][OP(H)(O)(OH)] (11) compounds are also described.
sulfido compounds. We have also demonstrated that these
NCN chelated organoantimony(III) and organobismuth-
(III) oxides can be utilized as starting materials for the con-
trolled and reliable preparation of organometallic molecu-
lar phosphonates.[3] In this way, we enriched the available
knowledge of similar group 15 compounds, which is at this
time still quite limited.[4] Studies dealing with this class of
Introduction
Recently, we have started investigating the preparation of
well-defined and soluble organoantimony(III) and organ-
obismuth(III) oxides and sulfides, which are stabilized by
coordination of the potentially tridentate NCN ligand[1]
[2,6-(Me2NCH2)2C6H3]–, denoted as L hereafter. The ox-
ides are dimeric, [LMO]2 (M = Sb, Bi), with a central four-
membered ring system, which is similar to the solid-state
structures discovered for the corresponding sulfides,
[LMS]2.[2] Interestingly, the sulfides were shown to be able
to dissociate in solution to give the monomeric compounds
that contained terminal metal–sulfur bonds, making them
reactive to other substrates such as sulfur or carbon disulf-
ide.[2c] The oxides are able to reversibly bind to carbon di-
oxide and react with trifluoromethanesulfonic acid with the
formation of an ionic hydroxido compound containing ter-
minal M–OH groups.[2b] These compounds are potential
starting materials for the preparation, under relatively mild
reaction conditions and starting from soluble and well-de-
fined precursors, of other main group element oxido and
[a] Department of General and Inorganic Chemistry, Faculty of
Chemical Technology, University of Pardubice,
Studentská 573, 53210 Pardubice, Czech Republic
Fax: +420-466-037-068
E-mail: libor.dostal@upce.cz
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201000746.
Scheme 1.
View this journal online at
wileyonlinelibrary.com
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Organoantimony(III) and Organobismuth(III) Phosphinates and Phosphites
1
compounds are often hampered by their limited solubility. detected in the H NMR spectra for compounds 5 and 6.
This problem seems to be solved in part by the presence of Doublet resonance peaks, corresponding to the PH groups,
ligand L in the compounds of this type.
at δ = 6.84 ppm (1JP,H = 653 Hz) for 5 and at δ = 7.07 ppm
As a part of an ongoing investigation of main group (1JP,H = 643 Hz) for 6, and broad singlets at low field [δ =
compounds containing potentially tridentate pincer-type li- 11.70 (5) and 10.61 ppm (6)] with integrated intensities of 2
gands, and as a logical continuation of studies in this field, that are attributable to POH groups, were observed in the
we report herein the syntheses, structures and reactivity of 1H NMR spectra, providing evidence for the proposed
organoantimony and organobismuth phosphinate and structures of 5 and 6. The 31P NMR spectra of 5 and 6
phosphite complexes (Scheme 1) that are stabilized by the revealed doublets at δ = 4.5 ppm (5) and 5.2 ppm (6). In
1
NCN chelating ligand L. Previously we were able to synthe- the H NMR spectrum of the organoantimony phosphite
size mixed phoshonate compounds (i.e. complexes contain- 7, the NCH2 group signal has an AX pattern, and two sing-
ing two different phosphonate groups),[3] and herein the lets were detected for the N(CH3)2 groups, which is consis-
syntheses of novel mixed phosphinate-phosphite, phos- tent with the ligand’s donor atoms being in a pseudo-cis
phonate-phoshinate and phosphonate-phosphite com- arrangement, as also determined from solid-state analyses
pounds are also described (Scheme 2).
(vide infra). Conversely, the corresponding signals in the 1H
NMR spectrum of the bismuth congener 8 are significantly
broader. In both cases, the presence of the PH groups was
established by the observation of doublet resonance peaks
both in the 1H NMR spectra at δ = 6.77 ppm (1JP,H
=
644 Hz) for 7 and 7.14 ppm (1JP,H = 595 Hz) for 8, and in
the 31P NMR spectra at δ = –0.5 ppm for 7 and 3.1 ppm
for 8. Any signals attributable to POH groups are absent
1
from the H NMR spectra of 7 and 8.
The characteristic vibrations for PH groups in the 2240–
2383 cm–1 regions of the IR spectra of compounds 3–8
proved the presence of this functionality in these complexes.
Similarly, strong bands were detected in the PO vibration
domain for all compounds. Both compounds 5 and 6 con-
tain POH groups in their structure, which was reflected by
observation of three broad bands (around 2700, 2300 and
1600 cm–1) in their IR spectra, and splitting of the POH
peaks points to strong hydrogen bonds between these POH
moieties.[3,5]
We have recently reported so-called mixed antimony(III)
and bismuth(III) phoshonates, in which two different phos-
phonate units are bonded to the same central ion.[3] We
have also suggested that an analogous synthetic protocol
may lead to similar phosphorus-antimony(bismuth) com-
pounds containing either two phosphorus ions in a +III
oxidation state, or with one phosphorus ion in a +III state
Scheme 2.
Results and Discussion
Syntheses and Characterization of Compounds 3–8
and the other in a +V state. Compound 7 showed a propen-
1
The reaction of oxides 1 and 2 with 4 mol-equiv. of phen- sity to react with acids, as demonstrated by a H and 31P
ylphosphinic acid in dichloromethane resulted in organo- NMR experiment, and when mixed with 2 equiv. of phos-
antimony (3) and organobismuth (4) phenylphosphinates phorous acid compound 5 was produced.[6] This fact made
(Scheme 1). The 1H NMR spectra of 3 and 4 in CDCl3 us study the reactivity of 7 in more detail. The reaction of
revealed one set of sharp signals (singlets) for the NCH2 phosphite 7 with 2 mol-equiv. of phenylphosphinic acid
and N(CH3)2 groups pointing to a symmetrical tridentate gave the mixed phosphite-phosphinate 9 (Scheme 2). The
coordination mode for the NCN ligand. The presence of a 1H and 13C NMR spectra of 9 revealed sets of sharp signals
1
PH group in the complexes was proven by observation in consistent with the proposed structure, the H NMR spec-
1
the H NMR spectra of a doublet resonance peak at δ = trum included two doublets corresponding to the phosphite
7.54 ppm (1JP,H = 531 Hz) for 3 and at δ = 7.67 ppm (1JP,H PH group at δ = 6.84 ppm (1JP,H = 656 Hz), a signal from
= 528 Hz) for 4, and doublets at δ = 13.7 ppm for 3 and at the PH group of the phenylphosphinate group at δ =
δ = 15.5 ppm for 4 were observed in the 31P NMR spectra 7.56 ppm (1JP,H = 536 Hz), and a broad signal at δ =
of these complexes. Treatment of oxides 1 and 2 with phos- 11.61 ppm attributable to the POH group. The 31P NMR
phorous acid gave, depending on the molar ratio used (1:4 spectrum revealed, as expected, two doublets at δ = 3.9 ppm
or 1:2), the secondary phosphites 5 and 6 or the fully depro- (phosphite) and 16.0 ppm (phenylphosphinate). The IR
tonated phosphites 7 and 8 (Scheme 1). One set of sharp spectrum of 9 revealed bands at 2380 and 2351 cm–1 corre-
signals (singlets) for the NCH2 and N(CH3)2 groups was sponding to the PH group, peaks at 2711, 2321, 1645 cm–1
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for the POH groups that point to possible hydrogen bond- tially tetrahedral. There are no significant intermolecular
ing,[5] and peaks at 1180, 1127, 977 cm–1 that are attribut- contacts in the solid-state structure of 3.
able to vibrations of the PO groups.
Attempts to obtain single crystals of compound 5 re-
With phosphonate 10[3] as a starting compound the sulted in an isomeric compound LSb[O2P(H)(O)][(HO)2P-
mixed phosphonate-phosphite compounds 11 and 12 can (H)(O)] (5a). The composition of 5 (Scheme 1) was formu-
be prepared, depending on which reagent is added, namely, lated, in accordance with the NMR spectroscopic data, as
1
phenylphosphinic or phosphorous acid (Scheme 2). The H containing two secondary phosphite groups that are only
and 13C NMR spectra of 11 and 12 are consistent with the partially deprotonated, but the composition of 5a (a single-
proposed structures. In the 1H NMR spectra the PH group crystalline material) must be described as containing one
signals were detected as doublets at δ = 7.59 ppm (1JP,H
=
fully deprotonated phosphite group that forms a solvate
536 Hz) for 11 and at δ = 6.84 ppm (1JP,H = 656 Hz) for 12. with phosphorous acid (Figure 2). The compositional dif-
The presence of POH moieties was reflected by observation ference between 5 and 5a is also reflected in their different
of broad singlets at 11.63 ppm for 11 and 11.57 ppm for 12. solid-state IR spectra (see Experimental Section), and the
The 31P NMR spectra for both compounds revealed one fact that the single crystals (5a) are totally insoluble in
singlet corresponding to the tert-butylphoshonate moiety CDCl3 (probably reflecting the high complexity of the
(at δ = 36.9 ppm for 11 and at δ = 36.3 ppm for 12) and structure due to the presence of an extensive hydrogen-bond
one double at δ = 16.3 ppm for 11 (phenylphosphinate) and network), in which polycrystalline 5 is very soluble. To shed
at δ = 6.3 ppm for 12 (phosphite). The IR spectra supported some light on this problem, we left compound 5 (after char-
the proposed structures for both compounds (see Experi- acterization by 1H, 13C and 31P NMR spectroscopy) in
mental Section).
dichloromethane for one week. A white insoluble precipi-
tate formed during this time, which was shown to be 5a by
the excellent agreement of the X-ray powder diffractogram
of this material with the simulated pattern determined from
Molecular Structures of 3, 5a and 7
Compound 3 crystallizes in space group P21/c, and its the single-crystal data (see the Supporting Information).
molecular structure with relevant structural parameters is These findings point, most probably, to the high fluxion-
depicted in Figure 1. Both phenylphosphinate groups are ality of the acidic POH hydrogen atoms when 5 is in solu-
coordinated to the central antimony ion in a unidentate tion, which leads to the crystallization (or precipitation) of
fashion with bond lengths of Sb1–O1 2.204(2) and Sb1– 5a.
O3 2.223(2) Å, and both functional groups are located in a
The structure of 5a (Figure 2) may be described as an
mutually trans fashion as demonstrated by the O1–Sb1–O3 aduct of a NCN chelated organoantimony phosphite with
angle of 163.87(7)°. The NCN ligand is coordinated in a phosphorous acid, but due to extensive hydrogen bonding
tridenate fashion to the central ion, and the bond lengths the complete structure is more complex. The monomeric
describing the Sb–N dative connection are Sb1–N1 2.460(3) unit is shown in Figure 2 (top). The central ion (Sb1) is
and Sb1–N2 2.400(3) Å. The coordination polyhedron coordinated by the NCN ligand in tridentate fashion
around the central metal atom may be described as a [the bond lengths are Sb1–N2 2.4262(19) and Sb1–N1
strongly distorted tetragonal pyramid with the ipso-carbon 2.4161(19) Å, and the bonding angle N1–Sb1–N2 is
atom (C1) at the apical position. The shapes of the coordi- 149.17(6)°]. The phosphite group, which is fully deproton-
nation polyhedra of the phosphorus atoms remain essen- ated, is coordinated to the central ion through oxygen atom
Figure 1. ORTEP diagram for compound 3 with the thermal displacement parameters at the 30% probability level. Hydrogen atoms,
except those bonded to phosphorus atoms, are omitted for clarity. Selected distances [Å] and angles [°]: Sb1–C1 2.109(2), Sb1–N1 2.460(3),
Sb1–N2 2.400(3), Sb1–O1 2.204(2), Sb1–O3 2.223(2), O1–P1 1.519(2), O2–P1 1.483(2), O3–P2 1.529(2), O4–P2 1.484(2), N1–Sb1–N2
149.44(7); C1–Sb1–N1 74.09(9), C1–Sb1–N2 75.42(9), C1–Sb1–O1 81.65(9), C1–Sb1–O3 82.22(9), O1–Sb1–O3 163.87(7).
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Organoantimony(III) and Organobismuth(III) Phosphinates and Phosphites
Figure 2. ORTEP diagram for compound 5a (top: monomeric unit; bottom: hydrogen-bond network) with the thermal displacement
parameters at 30% probability level. Hydrogen atoms, except those involved in hydrogen bonds and bonded to phosphorus atoms, are
omitted for clarity. Selected distances [Å] and angles [°]: Sb1–C1 2.105(3), Sb1–N1 2.4161(19), Sb1–N2 2.4262(19), Sb1–O3 2.2519(15),
Sb1–O4a 2.1961(17); C1–Sb1–N1 74.67(8), C1–Sb1–N2 74.52(8), C1–Sb1–O3 82.72(8), C1–Sb1–O4a 83.20(8), N1–Sb1–N2 149.17(6),
O1–Sb1–O4a 165.92(6). Symmetry operators: a: x, 1/2 – y, –1/2 + z; b: x, 1/2 – y, 1/2 + z; c: –1 + x, 1/2 – y, 1/2 + z; d: –1 + x, y, z; e:
1 – x, 1 – y, 1 – z; f: 1 – x, 1/2 + y, 3/2 – z; g: –x, –y, 2 – z; h: – x, 1/2 + y, 3/2 – z. Hydrogen-bond distances [Å] and angles [°]: O1···O2c
2.453(3), O5c···O6f 2.515(3), O6c···O5f 2.515(3), O1···H(O2c)–O2c 161, O5c···H(O6f)–O6f 154, O5f···H(O6c)–O6c 154.
O3 [the Sb1–O3 bond length is 2.2519(15) Å], and the sec- the P=O group of each phosphite entity within these infi-
ond deprotonated oxygen atom O4 is connected to the anti- nite chains is involved in a hydrogen bond with one of the
mony atom of a neighboring molecule [Sb1b in Figure 2 POH groups of the phosphorous acid, O1···H(O2c), the
(bottom)]. The coordination environment of the Sb1 atom length of this hydrogen bond (O–O distance) is 2.453(3) Å.
is completed by phopshite oxygen atom O4a [the bond Furthermore, the second POH group of the phoshorus acid
length Sb1–O4a is 2.1961(17) Å]. This bonding arrange- is connected to a neighboring acid molecule via by ad-
ment leads to the formation of an infinite chain structure ditional hydrogen bonds, O5c···H(O6f) and O5f···H(O6c);
with alternating LSb (Sb1a, Sb1 and Sb1b ions) and phos- both hydrogen bonds are 2.515(3) Å in length (O–O dis-
phite (P11a, P11 and P11b ions) fragments as shown in Fig- tance). The remaining POH group (O2f) of the second
ure 2 (bottom). The coordination polyhedron around each phosphorous acid is in turn bonded to atom O1g of a
antimony ion is best described as a distorted tetragonal neighboring infinite NCN chelated organoanitmony phos-
pyramid with the ipso-carbon atom located at the apex and phite chain. The complete structure may be summarized as
oxygen atoms in trans positions in the basal plane [the O3– infinite phosphite chains linked by dimers of phosphorous
Sb1–O4a angle is 165.92(6)°]. The third oxygen atom from acid that are held together by hydrogen bonds. This bond-
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ing arrangement is repeated throughout the whole structure dant arms of the ligand may play an important role in stabi-
leading to the formation of a polymeric structure contain- lizing the central ring, and hence are situated above it. The
ing alternating infinite antimony phosphite and phos- presence of the ligand bound in such a way hinders oligo-
phorous acid chains (see Figure S1 in the Supporting Infor- merization or polymerization of the phosphite complex.
mation).
Also of interest is the position of the hydrogen atoms, which
Compound 7 crystallizes in space group P2/c, and the are orientated in the same direction. Furthermore, only one
1
unit cell contains two independent molecules, the structures set of signals was observed in the solution H, 31P and 13C
of which are closely related. Only one molecule is depicted NMR spectra suggesting that only this compound isomer
in Figure 3, and relevant structural parameters are given in is present in solution, although the second isomer with a
the figure caption.
different orientation of the hydrogen atoms and oxygen
atoms O3 and O3a is possible.[7]
Decomposition Pathways for Organobismuth Phosphinates
Although antimony compounds 3, 5 and 7 are stable in
solution, the organobismuth compounds 4 and 8 have only
limited stability in solution. Leaving compounds 4 and 8
for a long time in solution results in a black precipitate
forming, which in part hampered attempts to obtain single
crystals of these compounds. This insoluble solid was
shown to be elemental bismuth suggesting that a redox pro-
cess is taking place in solutions of these bismuth com-
pounds.
Interestingly, Shimada et al. have recently reported the
reaction of a CNC chelated organobismuth oxide (where
the CNC ligand was 5,6,7,12-tetrahydrodibenz[c,f][1,5]aza-
bismocine, Figure 4, denoted LЈ hereafter) with Ph2P(O)(H)
(in which phosphorus is in the +III oxidation state). The
reaction proceeded as a redox process yielding the reduced
compound LЈBiBiLЈ that contained a Bi–Bi bond and in
which the phoshorus ions were oxidized to the V+ state,
which led to the formation of the organobismuth phosphi-
nate LЈBiOP(O)(Ph2).[8] Taking this fact into account, our
Figure 3. ORTEP diagram for compound 7 (only one of the two
independent molecules is shown) with the thermal displacement
parameters at the 30% probability level. Hydrogen atoms, except
those bonded to phosphorus atoms and dichloromethane mole- compounds may decompose by the same pathway giving
cules, are omitted for clarity. Symmetry operator: a: 1 – x, y, 1/2 –
organobismuth(I) compounds and the corresponding or-
z. Selected distances [Å] and angles [°]: Sb1–C1 2.117(7), Sb1–N1
ganobismuth phosphonate complexes. To test this possibil-
2.613(5), Sb1–N2 2.543(7), Sb1–O1 2.075(5), Sb1–O2a 2.082(5),
ity the decomposition of compound 4 (which seemed to de-
O1–P1 1.527(5), O2–P1 1.543(5), O3–P1 1.474(5); N1–Sb1–N2
compose easily) was studied in more detail, and the reaction
of the oxide 2 with Ph2P(O)(H) was investigated and per-
formed in a similar manner to Shimada et al.’s experiment.
121.2(2), C1–Sb1–N1 71.2(3), C1–Sb1–N2 72.1(2), C1–Sb1–O1
91.0(2), C1–Sb1–O2a 91.2(2), O1–Sb1–O2a 81.9(2), O1–P1–O2
111.7(3), O1–P1–O3 113.3(3), O2–P1–O3 127.7(2).
Compound 7 has a dinuclear molecular structure with a
central eight-membered Sb2P2O4 ring that has a boat con-
formation. This ring is a consequence of two phosphite
groups, which are fully deprotonated, forming bridges be-
tween two antimony ions. These bridges are nearly symmet-
rical as demonstrated by the bond lengths Sb1–O1 2.075(5)
and Sb1a–O2 2.082(5) Å. The angles involving the anti-
Figure 4. Structure of 5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine
ligand.
Compound 4 was heated in toluene to 60 °C, and within
mony ions within the ring (O1–Sb1–O2a 81.9(2)° and its a few hours the solution started to change color and be-
symmetry-equivalent) are significantly more acute than the came slightly violet. This may suggest the presence of a re-
angles incorporating the phosphorus atoms; the O1–P1–O2 duced bismuth(I) compound in the solution, but this is un-
angle is 111.7(3)°. The NCN ligand is coordinated in a trid- stable under these reaction conditions, and metallic bismuth
enate fashion to the central ion [the bond lengths are Sb1– was characterized by X-ray powder diffraction as the de-
N1 2.613(5) and Sb1–N2 2.543(7) Å], but in contrast to composition product after workup.[9–11] The 1H NMR spec-
compounds 3 and 5a where the donor atoms are in a trans tra of the reaction mixture revealed, besides signals associ-
position, in 7 it is bound in a pseudo-cis fashion with the ated with the starting compound 4, signals that can be as-
N1–Sb1–N2 angle equal to 121.2(2)°. The coordinated pen- signed to the free ligand that is a decomposition coproduct
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Organoantimony(III) and Organobismuth(III) Phosphinates and Phosphites
Scheme 3.
of the bismuth(I) compound, and eventually a new set of pound that gave a signal at δ = 5.1 ppm in the 31P NMR
signals emerge that are attributable to the phosphonate spectra was detected, but this signal disappeared over time,
LBi[OP(Ph)(O)(OH)]2 (13). Similarly, the 31P NMR spectra and the structure of this compound remains unknown.
revealed, in addition to the doublet resonance peak associ- Compound 13 was also prepared by the conventional reac-
ated with 4 (δ = 15.5 ppm, 1JH,P = 528 Hz), an extra singlet tion of oxide 2 with 2 equiv. of phenylphosphonic acid, the
1
at δ = 14.8 ppm with the lost of JP,H coupling, which pro- analysis data for the product of this reaction coincided with
vides evidence for the oxidation of the phosphorus ion to all the analytical data for compound 13 that was formed
the +V state and the formation of 13. This singlet increased from the decomposition of 4.
in intensity over time giving ca. 30% conversion after 16 d
Mixing oxide 2 and Ph2P(O)(H) in 3:4 molar ratio in
(Figure 5). In the very early stages of the reaction, a com- C6D6 at room temp. resulted in the reaction solution imme-
diately exhibiting an intense violet color, which was fol-
lowed by the precipitation of bismuth metal (Scheme 3).
The reaction was monitored by 31P NMR spectroscopy (see
the Supporting Information), and the spectra revealed a
doublet resonance peak associated with the starting mate-
1
rial Ph2P(O)(H) (δ = 17.2 ppm, JP,H = 462 Hz) and a sing-
let (δ = 21.3 ppm) that corresponds to the product 14,
which contains an oxidized phosphorus ion. The reaction
at room temp. is completed within 2 d as shown by the 31P
NMR spectra in which only signals from 14 are observed
1
after this time. The H NMR spectrum contained, besides
the signal associated with 14, signals arising from the free
ligand. Compound 14 was also prepared by the direct reac-
tion of oxide 2 with diphenylphosphonic acid.
Conclusions
The NCN chelating ligand L has been shown to be very
efficient at stabilizing various types of organoantimony and
organobismuth compounds that contain different types of
oxido-phosphorus substituents. In most cases the com-
pounds retain their discrete molecular structures and do not
tend to oligomerize or polymerize (except 5a), which pro-
motes their solubility in organic solvents such as chloro-
form and dichloromethane. An investigation focused
towards the targeted synthesis of other mixed antimony(bis-
muth)-oxido compounds containing elements other than
phosphorus are currently underway in our laboratories.
Figure 5. 31P NMR spectra recorded to monitor the decomposition
of compound 4 to give compound 13: (A) at the start of the reac-
tion – pure 4; (B) after 30 min; (C) after 16 d; (D) compound 13
prepared from the reaction of 2 with phenylphosphonic acid. The
Experimental Section
inset spectra are 31P{1H} NMR data that show the coalescence of
the signals that are split in the 31P NMR spectra due to the pres-
ence of the PH group.
General Procedures: All air- and moisture-sensitive manipulations
were carried out under argon with standard Schlenk tube tech-
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1
niques. All solvents were dried by standard procedures and distilled
4.00 (s, 4 H, NCH2), 6.84 (d, JP,H = 653 Hz, 2 H, PH), 7.19 (d, 2
prior to use. H, 13C and 31P NMR spectra were recorded with a
H, Ar-H3,5), 7.33 (t, 1 H, Ar-H4), 11.7 [s (br.), 2 H, POH] ppm.
13C NMR (100.61 MHz, CDCl3, 25 °C): δ = 46.4 [s, N(CH3)2], 64.4
(s, NCH2), 125.4 (s, Ar-C3,5), 130.3 (s, Ar-C4), 144.0 (s, Ar-C2,6),
1
Bruker AMX360 spectrometer, with a 5 mm tunable broad-band
probe. The shifts of the peaks in the 1H and 13C NMR spectra
were measured relative to the residual signals of the solvent
155.4 (s, Ar-C1) ppm. 31P NMR (161.98 MHz, CDCl3, 25 °C): δ =
[CDCl3: δ(1H) = 7.27 ppm and δ(13C) = 77.23 ppm; C6D5: δ(1H) = 4.5 (d, JP,H = 653 Hz, PH) ppm. IR: ν = 2800 (m), 2383 (s), 1637
1
˜
7.16 ppm]. The shift of the peaks in the 31P NMR spectra were
measured relative to an external standard, 85% H3PO4, δ(31P) =
0.00 ppm. IR spectra were recorded over the 5000–400 cm–1 range,
with the samples prepared as KBr pellets or as nujol mulls (10),
with a Nicolet Magna 550 FT-IR spectrometer. The starting com-
pounds: phenylphosphinic acid, diphenylphosphonic acid, phos-
phorous acid and diphenylphosphane oxide, were obtained from
commercial suppliers and used as delivered. Compounds [2,6-
(s br., POH), 2240 (m, PH), 1177 (vs), 1009 (vs br., PO) cm–1.
To obtain isomeric compound 5a a clear dichloromethane (5 mL)
solution of 5 was stirred for 24 h. During this period a white pre-
cipitate formed, which was filtered off and washed with hexane
(15 mL). The remaining white powder was characterized as 5a by
powder X-ray diffraction (see the Supporting Information; it is
noteworthy that the filtrate does not contain any significant
amount of the NCN chelated compound, which suggests exclusive
(2) conversion of 5 to 5a). The yield based on the starting material 5
[2a]
[2b]
(Me2NCH2)2C6H3SbO]2
(1), [2,6-(Me2NCH2)2C6H3BiO]2
and 2,6-(Me2NCH2)2C6H3Sb[O2P(O)tBu][3] (12) were prepared ac-
was 90%; m.p. 148 °C. IR: ν = 2711 (vs), 2326 (m sh), 1630 (m,
˜
cording to literature procedures.
POH), 2383 (m, PH), 1030 (vs), 1005 (vs, PO) cm–1.
C12H23N2O6P2Sb (475.03): calcd. C 30.3, H 4.9; found C 30.4, H
5.2.
2,6-(Me2NCH2)2C6H3Sb[OP(H)(O)Ph]2 (3): A dichloromethane
(10 mL) solution of [2,6-(Me2NCH2)2C6H3SbO]2 (1) (79 mg,
0.12 mmol) was added to a suspension of phenylphosphinic acid
(68 mg, 0.48 mmol) in dichloromethane (15 mL), and the resulting
mixture was stirred at room temperature for 2 h. The reaction mix-
ture was concentrated in vacuo, and the residue was washed with
hexane (5 mL). The remaining white solid was recrystallized from
a dichloromethane/toluene mixture to give 3 as white crystals
(103 mg, 72%); m.p. 149 °C (dec.). 1H NMR (400 MHz, CDCl3,
2,6-(Me2NCH2)2C6H3Bi[OP(H)(O)(OH)]2 (6): Compound 6 was
prepared according to a similar procedure as described for the syn-
thesis of compound 3. A dichloromethane (10 mL) solution of [2,6-
(Me2NCH2)2C6H3BiO]2 (2) (124 mg, 0.149 mmol) was mixed with
phosphonic acid (49 mg, 0.59 mmol) in dichloromethane (15 mL)
to give 6 as white crystals (108 mg, 64%); m.p. 133 °C (dec.). 1H
NMR (400 MHz, CDCl3, 25 °C): δ = 2.90 [s, 12 H, N(CH3)2], 4.35
1
25 °C): δ = 2.62 [s, 12 H, N(CH3)2], 4.00 (s, 4 H, NCH2), 7.20 (d, (s, 4 H, NCH2), 7.07 (d, JP, H = 643 Hz, 2 H, PH), 7.52 (t, 1 H,
2 H, Ar-H3,5), 7.35 (m, 7 H, Ph-H3,4,5 and Ar-H4), 7.53 (m, 4 Ar-H4), 7.72 (d, 2 H, Ar-H3,5), 10.61 [s (br.), 2 H, POH] ppm. 13
C
1
H, Ph-H2,6) 7.54 (d, JP,H = 531 Hz, 2 H, PH) ppm. 13C NMR
NMR (100.61 MHz, CDCl3, 25 °C): δ = 46.7 [s, N(CH3)2], 68.5 (s,
(100.61 MHz, CDCl3, 25 °C): δ = 46.6 [s, N(CH3)2], 64.5 (s, NCH2), NCH2), 128.1 (s, Ar-C3,5), 129.8 (s, Ar-C4), 152.3 (s, Ar-C2,6)
125.4 (s, Ar-C3,5), 128.3 [d, 3JP,C = 13 Hz, Ph-C3,5], 129.9 (d, 2JP, C ppm, an Ar-C1 signal was not observed. 31P NMR (161.98 MHz,
1
= 12 Hz, Ph-C2,6), 130.5 (s, Ar-C4), 131.3 (s, Ph-C4), 136.4 (d, CDCl3, 25 °C): δ = 5.2 (d, JP,H = 643 Hz, PH) ppm. IR: ν = 2701
˜
1JP,C = 128 Hz, Ph-C1) 143.7 (s, Ar-C2,6), 155.3 (s, Ar-C1) ppm.
(m br.), 2244 (m br.), 1641 (s br., POH), 2383 (vs, PH), 1152 (vs),
1006 (vs br., PO) cm–1. C12H23BiN2O6P2 (562.25): calcd. C 25.6, H
4.1; found C 25.7, H 4.3.
1
31P NMR (161.98 MHz, CDCl3, 25 °C): δ = 13.7 (d, JH,P
=
531 Hz, PH) ppm. IR: ν = 2323 (s), 2305 (s, PH), 1205 (vs), 1123 (s,
˜
PO) cm–1. C24H31N2O4P2Sb (595.22): calcd. C 48.4, H 5.3; found C
48.5, H 5.5.
2,6-(Me2NCH2)2C6H3Sb[O2P(O)(H)] (7): Compound 7 was pre-
pared according to a similar procedure as described for the synthe-
sis of compound 3. A dichloromethane (10 mL) solution of [2,6-
(Me2NCH2)2C6H3SbO]2 (1) (101 mg, 0.153 mmol) was mixed with
phosphonic acid (25 mg, 0.307 mmol) in dichloromethane (15 mL)
to give 5 as white crystals (82 mg, 68%); m.p. 243 °C (dec.). 1H
2,6-(Me2NCH2)2C6H3Bi[OP(H)(O)Ph]2 (4): Compound 4 was pre-
pared according to a similar procedure as described for the synthe-
sis of compound 3. A dichloromethane (10 mL) solution of [2,6-
(Me2NCH2)2C6H3BiO]2 (2) (105 mg, 0.126 mmol) was mixed with
phenylphosphinic acid (72 mg, 0.504 mmol) in dichloromethane
(15 mL) to give 4 as white crystals (118 mg, 69%); m.p. 139 °C
NMR (400 MHz, CDCl3, 25 °C): δ = 2.02 [s (br.), 6 H, N(CH3)2],
2.77 [s (br.), 6 H, N(CH3)2] 3.13 and 4.77 (AX pattern, JH,H
2
=
(dec.). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 2.74 [s, 12 H, 13 Hz, 4 H, NCH2), 6.77 (d, JP,H = 644 Hz, 1 H, PH), 7.06 (br., 2
N(CH3)2], 4.36 (s, 4 H, NCH2), 7.34 (m, 6 H, Ph-H3,4,5), 7.54 (m,
H, Ar-H3,5), 7.11 (br., 1 H, Ar-H4) ppm. 13C NMR (100.61 MHz,
5 H, Ph-H2,6 and Ar-H4), 7.67 (d, JP,H = 528 Hz, 2 H, PH), 7.73 CDCl3, 25 °C): δ = 41.1 [s, N(CH3)2], 44.6 [s, N(CH3)2], 62.4 (s,
1
1
(d, 2 H, Ar-H2,6) ppm. 13C NMR (100.61 MHz, CDCl3, 25 °C): δ
NCH2), 125.1 (s, Ar-C3,5), 128.8 (s, Ar-C4), 146.8 (s, Ar-C2,6),
= 46.9 [s, N(CH3)2], 68.6 (s, NCH2), 128.3 (s, Ar-C3,5), 128.4 (d, 152.1 (s, Ar-C1) ppm. 31P NMR (161.98 MHz, CDCl3, 25 °C): δ =
3JP,C = 13 Hz, Ph-C3,5), 129.9 (s, Ar-C4), 130.1 (d, JP,C = 11 Hz
–0.5 (d, 1JP,H = 644 Hz, PH) ppm. IR: ν = 2355 (vs), 2319 (m, PH),
2
˜
4
1
Ph-C2,6), 131.1 (d, JP,C = 4 Hz, Ph-C4), 137.6 (d, JP,C = 128 Hz,
1199 (m), 1027 (vs), 1006 (vs), 981 (s, PO) cm–1. C12H20N2O3PSb
(393.03): calcd. C 36.7, H 5.1; found C 36.5, H 4.9.
Ph-C1), 152.1 (s, Ar-C2,6) ppm, an Ar-C1 signal was not observed.
1
31P NMR (161.98 MHz, CDCl3, 25 °C): δ = 15.5 (d, JH,P
=
2,6-(Me2NCH2)2C6H3Bi[O2P(H)(O)] (8): Compound 8 was pre-
pared according to a similar procedure as described for the synthe-
sis of compound 3. A dichloromethane (10 mL) solution of [2,6-
(Me2NCH2)2C6H3BiO]2 (2) (68 mg, 0.082 mmol) was mixed with
phosphonic acid (13 mg, 0.163 mmol) in dichloromethane (15 mL)
to give 8 as white crystals (56 mg, 72%); m.p. 198 °C (dec.). 1H
NMR (400 MHz, CDCl3, 25 °C): δ = 2.78 [s, 12 H, N(CH3)2], 4.25
528 Hz, PH) ppm. IR: ν = 2283 (m, PH), 1176 (s), 1130 (s, PO)
˜
cm–1. C24H31BiN2O4P2 (682.44): calcd. C 42.2, H 4.6; found C 42.4,
H 4.8.
2,6-(Me2NCH2)2C6H3Sb[OP(H)(O)(OH)]2 (5): A dichloromethane
(10 mL) solution of [2,6-(Me2NCH2)2C6H3SbO]2 (1) (103 mg,
0.16 mmol) was added to a suspension of phosphorous acid (51 mg,
0.63 mmol) in dichloromethane (15 mL), and the mixture was (s, 4 H, NCH2), 7.14 (d, 1JP,H = 595 Hz, 1 H, PH), 7.41 (t, 1 H, Ar-
stirred for 30 min. Concentration of the solution and washing with
H4), 7.60 (d, 2 H, Ar-H3,5) ppm. 13C NMR (100.61 MHz, CDCl3,
hexane (10 mL) gave 5 as white crystals (108 mg, 71%); m.p. 93 °C.
25 °C): δ = 46.8 [s, N(CH3)2], 68.6 (s, NCH2), 127.9 (s, Ar-C3,5),
1H NMR (400 MHz, CDCl3, 25 °C): δ = 2.80 [s, 12 H, N(CH3)2], 129.1 (s, Ar-C4), 152.1 (s, Ar-C2,6) ppm, an Ar-C1 signal was not
5228
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 5222–5230

Organoantimony(III) and Organobismuth(III) Phosphinates and Phosphites
observed. 31P NMR (161.98 MHz, CDCl3, 25 °C): δ = 3.1 (d, 1JP,H
C1 signal was not observed. 31P NMR (161.98 MHz, CDCl3,
= 595 Hz, PH) ppm. IR: ν = 2323 (s, PH), 1010 (vs), 1002 (s, PO) 25 °C): δ = 6.3 (d, 1JH,P = 656 Hz, PH), 36.3 (s) ppm. IR: ν = 2708
˜
˜
(m br.), 2370 (s br.), 1655 (s br., POH), 2346 (s, PH), 1262 (s), 1127
(vs), 1095 (vs), 980 (vs, PO) cm–1. C16H31N2O6P2Sb (531.13): calcd.
C 36.2, H 5.9; found C 36.4, H 6.1.
cm–1. C12H20BiN2O3P (480.25): calcd. C 30.0, H 4.2; found C 30.2,
H 4.4.
2,6-(Me2NCH2)2C6H3Sb[OP(H)(O)(OH)][OP(H)(O)(Ph)] (9):
A
dichloromethane (10 mL) solution of 2,6-(Me2NCH2)2C6H3Sb- 2,6-(Me2NCH2)2C6H3Bi[OP(O)(OH)Ph]2 (13): A dichloromethane
[O2P(O)(H)] (7) (33 mg, 0.084 mmol) was added to a suspension
of phenylphosphinic acid (12 mg, 0.084 mmol) in dichloromethane
(15 mL). The reaction mixture was stirred at room temperature for
3 h and then concentrated in vacuo and the residue washed with
hexane (5 mL). The product was recrystallized from a dichloro-
methane/hexane mixture. The resulting product was dried to give a
(10 mL) solution of [2,6-(Me2NCH2)2C6H3BiO]2 (2) (80 mg,
0.096 mmol) was added to a suspension of phenylphosphonic acid
(61 mg, 0.384 mmol) in dichloromethane (15 mL). The reaction
mixture was stirred at room temperature for 3 h. The reaction mix-
ture was concentrated in vacuo, and the residue was washed with
hexane (5 mL). The remaining white solid was recrystallized from
white solid (37 mg, 84%); m.p. 99 °C. 1H NMR (400 MHz, CDCl3, a dichloromethane/hexane mixture to give 13 as white crystals
25 °C): δ = 2.70 [s, 12 H, N(CH3)2], 4.01 (s, 4 H, NCH2), 6.84 (d, (99 mg, 72%); m.p. Ͼ 300 °C. 1H NMR (400 MHz, CDCl3, 25 °C):
1JP, H = 656 Hz, 1 H, PH) 7.20 (d, 2 H, Ar-H3,5), 7.40 (m, 4 H,
δ = 2.78 [s, 12 H, N(CH3)2], 4.29 (s, 4 H, NCH2), 7.20 (m, 4 H,
Ph-H3,4,5 and Ar-H4), 7.56 (d, 1JP,H = 536 Hz, 1 H, PH), 7.57 (m, Ph-H3,5), 7.30 (t, 2 H, Ph-H4), 7.47 (t, 1 H, Ar-H4), 7.60 (m, 4 H,
H, Ph-H2,6), 11.61 (br.,
H, POH) ppm. 13C NMR Ph-H2,6), 7.67 (d, 2 H, Ar-H3,5), 10.64 (br., 2 H, POH) ppm. 13C
(100.61 MHz, CDCl3, 25 °C): δ = 46.7 [s, N(CH3)2], 64.6 (s, NCH2), NMR (100.61 MHz, CDCl3, 25 °C): δ = 46.6 [s, N(CH3)2], 68.4 (s,
125.5 (s, Ar-C3,5), 128.5 (d, 3JP,C = 13 Hz, Ph-C3,5), 130.2 (d, 2JP,C
NCH2), that was overlapped with the Ph-C3,5 signal (s, Ar-C3,5),
= 12 Hz, Ph-C2,6), 130.5 (s, Ar-C4), 131.6 (s, Ph-C4), 136.4 (d, 128.0 (d, JP,C = 15 Hz, Ph-C3,5), 129.4 (s, Ar-C4), 130.2 (s, Ph-
2
1
3
1JP,C = 131 Hz, Ph-C1), 144.0 (s, Ar-C2,6), 155.5 (s, Ar-C1) ppm.
31P NMR (161.98 MHz, CDCl3, 25 °C): δ = 3.9 (d, 1JH,P = 656 Hz, Ph-C1), 152.4 (s, Ar-C2,6) ppm, an Ar-C1 signal was not observed.
PH), 16.0 (d, 1JH,P = 536 Hz, PH) ppm. IR: ν = 2711 (m br.), 2321 31P NMR (161.98 MHz, CDCl , 25 °C): δ = 14.8 (s) ppm. IR: ν =
C4), 130.9 (d, JP,C = 11 Hz, Ph-C2,6), 135.7 (d, JP,C = 103 Hz,
2
1
˜
˜
3
(s br.), 1645 (s br., POH), 2380 (s), 2351 (m, PH), 1180 (s br.), 1127 2708 (m br.), 2359 (s br.), 2337 (s br.), 1647 (s br., POH), 1135 (vs),
(s), 977 (vs, PO) cm–1. C18H27N2O5P2Sb (535.12): calcd. C 40.4, H
5.1; found C 40.5, H 5.3.
1110 (vs), 1002 (vs), 910 (vs, PO) cm–1. C24H31BiN2O6P2 (714.44):
calcd. C 40.3, H 4.4; found C 40.1, H 4.3.
2,6-(Me2NCH2)2C6H3Sb[OP(tBu)(O)(OH)][OP(H)(O)(Ph)] (11): 2,6-(Me2NCH2)2C6H3Bi[OP(O)(Ph)2]2 (14): A toluene (20 mL)
A dichloromethane (10 mL) solution of 2,6-(Me2NCH2)2C6H3Sb-
[O2P(O)tBu] (10) (28 mg, 0.062 mmol) was added to a suspension
of phenylphosphinic acid (8.8 mg, 0.062 mmol) in dichloromethane
(15 mL). The reaction mixture was stirred at room temperature for
3 h. The reaction mixture was concentrated in vacuo, and the resi-
due was washed with hexane (5 mL). The resulting product was
dried to give a white solid (32 mg, 86%); m.p. 147 °C. 1H NMR
solution of [2,6-(Me2NCH2)2C6H3BiO]2 (2) (132 mg, 0.159 mmol)
was added to a toluene (20 mL) solution of diphenylphosphane
oxide (43 mg, 0.212 mmol), and the resulting mixture was stirred
at room temperature for 12 h. The reaction mixture was filtered,
and the toluene filtrate was concentrated in vacuo, and the residue
was washed with hexane (5 mL). The resulting product was dried to
give a white solid (35 mg, 52%); m.p. 137 °C. 1H NMR (400 MHz,
CDCl3, 25 °C): δ = 2.56 [s, 12 H, N(CH3)2], 4.33 (s, 4 H, NCH2),
3
(400 MHz, CDCl3, 25 °C): δ = 1.10 (d, JP,H = 16 Hz, 9 H, tBuP),
2.74 [s, 12 H, N(CH3)2], 3.98 (s, 4 H, NCH2), 7.20 (d, 2 H, Ar- 7.27 (m, 12 H, Ph-H3,4,5), 7.60 (m, 9 H, Ph-H2,6 and Ar-H4), 7.76
1
1
H3,5), 7.41 (m, 4 H, Ph-H3,4,5 and Ar-H4), 7.59 (d, JP,H
=
(d, 2 H, Ar-H2) ppm. H NMR (400 MHz, C6D6, 25 °C): δ = 2.32
536 Hz, 1 H, PH), 7.59 (m, 2 H, Ph-H2,6), 11.63 (br., 1 H, POH) [s, 12 H, N(CH3)2], 3.95 (s, 4 H, NCH2), 7.04 (m, 12 H, Ph-H3,4,5),
ppm. 13C NMR (100.61 MHz, CDCl3, 25 °C): δ = 25.2 (s, CH3),
7.26 (Ar-H4), 7.37 (d, 2 H, Ar-H2), 7.88 (m, 8 H, Ph-H2,6) ppm.
1
31.0 (d, JP,C = 143 Hz, CP), 46.6 [s, N(CH3)2], 64.6 (s, NCH2), 13C NMR (100.61 MHz, CDCl3, 25 °C): δ = 46.9 [s, N(CH3)2], 68.5
125.2 (s, Ar-C3,5), 128.5 (d, 3JP,C = 13 Hz, Ph-C3,5), 130.3 (d, 2JP,C
(s, NCH2), 128.0 (d, JP,C = 13 Hz, Ph-C3,5), 128.1 (s, Ar-C3,5),
3
3
2
= 12 Hz, Ph-C2,6) that overlapped with the Ar-C4 signal at 131.5
129.5 (s, Ar-C4), 130.2 (d, JP,C = 3 Hz, Ph-C4), 131.2 (d, JP,C =
4
1
1
(s, JP,C = 2 Hz, Ph-C4), 136.3 (d, JP,C = 128 Hz, Ph-C1), 144.1
10 Hz, Ph-C2,6), 139.0 (d, JP,C = 131 Hz, Ph-C1), 152.3 (s, Ar-
C2,6) ppm, an Ar-C1 signal was not observed. 31P NMR
(161.98 MHz, CDCl3, 25 °C): δ = 21.1 (s) ppm. 31P NMR
(s, Ar-C2,6) ppm, an Ar-C1 signal was not observed. 31P NMR
(161.98 MHz, CDCl3, 25 °C): δ = 16.3 (d, JH,P = 536 Hz, PH),
1
36.9 (s) ppm. IR: ν = 2707 (m br.), 2337 (s), 1648 (s br., POH),
(161.98 MHz, C D , 25 °C): δ = 21.3 (s) ppm. IR: ν = 1181 (s),
˜
6 3
˜
2358 (s, PH), 1263 (s), 1127 (vs), 1095 (vs), 977 (vs, PO) cm–1. 1117 (vs), 988 (vs, PO) cm–1. C36H39BiN2O4P2 (834.63): calcd. C
C22H35N2O5P2Sb (591.23): calcd. C 44.7, H 6.0; found C 44.5, H 51.8, H 4.7; found C 52.0, H 4.5.
6.2.
X-ray Crystallography: Suitable single crystals of complexes 3, 5a,
2,6-(Me2NCH2)2C6H3Sb[OP(tBu)(O)(OH)][OP(H)(O)(OH)] (12): and 7 were mounted on glass fibers with oil and measured with a
Compound 12 was prepared according to a similar procedure as
described for the synthesis of compound 11. A dichloromethane
four-circle KappaCCD diffractometer equipped with a CCD area
detector, with monochromated Mo-Kα radiation (λ = 0.71073 Å) at
(10 mL) solution of 2,6-(Me2NCH2)2C6H3Sb[O2P(O)tBu] (12) 150(1) K. Numerical absorption corrections[12] based on the crystal
(59 mg, 0.131 mmol) was mixed with phosphonic acid (11 mg,
shapes were applied to the data for all crystals. The structures were
solved by direct methods (SIR92)[13] and refined by a full-matrix
least-squares procedure based on F2 (SHELXL97).[14] Hydrogen
0.131 mmol) in dichloromethane (15 mL) to give 12 as white crys-
tals (59 mg, 85%); m.p. 211 °C (dec.). 1H NMR (400 MHz, CDCl3,
3
25 °C): δ = 1.03 (d, JP,H = 16 Hz, 9 H, tBuP), 2.83 [s, 12 H, atoms were fixed at idealized positions in the crystallographic mod-
1
N(CH3)2], 3.98 (s, 4 H, NCH2), 6.84 (d, JP,H = 656 Hz, 1 H, PH),
7.20 (d, 2 H, Ar-H3,5), 7.34 (t, 1 H, Ar-H4), 11.57 (br., 2 H, POH)
els (riding model) and assigned temperature factors of Hiso(H) =
1.2Ueq(pivot atom) or, in the case of the methyl moieties, with
Hiso(H) = 1.5Ueq(methyl C). The C–H bond lengths were fixed at
ppm. 13C NMR (100.61 MHz, CDCl3, 25 °C): δ = 25.2 (s, CH3),
1
31.0 (d, JP,C = 146 Hz, CP), 46.5 [s, N(CH3)2], 64.4 (s, NCH2), 0.96, 0.97, and 0.93 Å for the methyl, methylene, and aromatic ring
125.1 (s, Ar-C3,5), 130.1 (s, Ar-C4), 143.9 (s, Ar-C2,6) ppm, an Ar-
groups, respectively, and at 0.83 Å for the O–H bonds. The final
Eur. J. Inorg. Chem. 2010, 5222–5230
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5229

T. Svoboda, R. Jambor, A. Ru˚zicˇka, Z. Padeˇlková, M. Erben, L. Dostál
ˇ
FULL PAPER
48, 10495–10497; d) H. J. Breunig, L. Koenigsmann, E. Lork,
M. Nema, N. Philipp, C. Silvestru, A. Soran, R. A. Varga, R.
Wagner, Dalton Trans. 2008, 1831–1842.
difference maps displayed no peaks of chemical significance as the
highest peaks and holes are close (ca. 1 Å) to the locations of heavy
atoms in the structures. CCDC-772345 (3), -772346 (5a), -772347
(7) contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[3]
[4]
T. Svoboda, R. Jambor, A. Ru˚zicˇka, Z. Padeˇlková, M. Erben,
ˇ
R. Jirásko, L. Dostál, Eur. J. Inorg. Chem. 2010, 1663–1669.
For other examples of similar group 15 compounds, see: a)
G. E. Graves, J. R. van Wazer, J. Organomet. Chem. 1978, 150,
233–237; b) G. E. Graves, J. R. van Wazer, J. Organomet. Chem.
1977, 131, 31–34; c) C. Silvestru, A. Silvestru, I. Haiduc, D. B.
Sowerby, K. H. Ebert, H. J. Breunig, Polyhedron 1997, 16,
2643–2649 and references cited therein; d) M. A. Said, K. C. K.
Swamy, D. M. Poojary, A. Clearfield, M. Veith, V. Huch, Inorg.
Chem. 1996, 35, 3235–3241; e) M. N. Gibbons, D. B. Sowerby,
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Crystallographic Data for 3: C24H31N2O4P2Sb, M = 595.20, mono-
clinic, P21/c, a = 9.2519(7), b = 21.1840(13), c = 14.4701(12) Å, β
= 117.382(7), V = 2518.3(4) Å3, Z = 4, T = 150(1) K, 21311 total
reflections, 5759 independent reflections [Rint = 0.049, R1(obs.
data) = 0.030, wR2(all data) = 0.051].
Crystallographic Data for 5a: C12H23N2O6P2Sb, M = 474.95, mo-
noclinic, P21/c, a = 8.9871(4), b = 16.9291(6), c = 12.2810(7) Å, β
= 106.332(5), V = 1793.08(14) Å3, Z = 4, T = 150(1) K, 13630
total reflections, 4092 independent reflections [Rint = 0.032, R1(obs.
data) = 0.024, wR2(all data) = 0.045].
Crystallographic Data for 7: C26H44Cl4N4O6P2Sb2, M = 955.89,
monoclinic, P2/c,
a = 22.6501(19), b = 6.1611(6), c =
27.6080(12) Å, β = 109.008(7)°, V = 3642.6(5) Å3, Z = 4, T =
150(1) K, 46669 total reflections, 8306 independent reflections [Rint
= 0.038, R1(obs. data) = 0.058, wR2(all data) = 0.1180].
ˇ
[5]
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Similar reactions for the bismuth analogues were not studied
due to the limited stability of bismuth phosphinates and phos-
phites in solution.
We also cannot rule out the possibility of fast dynamic pro-
cesses occurring in solution, which may involve the opening of
the ring and rotation of the phosphite group around an Sb–O–
P unit, which may enable conversion between isomers.
S. Shimada, J. Maruyama, Y.-K. Choe, T. Yamashita, Chem.
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Recently, we have reported organoantimony(I) compounds
containing ligand L (see ref.[10]), but our attempts to prepare
the analogous bismuth compounds, which would be stable at
ambient temperature, failed. The black insoluble material ob-
served after the reaction between 2 and Ph2P(O)(H) (or from
the decomposition of compound 4) was shown to be, by X-ray
powder diffraction, Bi (PDF No. 04-006-7762 see ref.[11]).
Supporting Information (see footnote on the first page of this arti-
cle): Figures showing the polymeric structure and X-ray powder
1
diffractogram of 5a, H and 31P NMR spectra of compounds 5, 9,
10 and 11, and 31P NMR spectra recorded to monitor the reaction
between compound 2 and Ph2P(O)(H).
[7]
[8]
[9]
Acknowledgments
The authors would like to thank the Grant Agency of the Czech
Republic (P106/10/0443) and the Ministry of Education of the
Czech Republic (MSM 0021627501 and LC523) for financial sup-
port. We would like to thank reviewers of the first version of this
paper for interesting and stimulating suggestions that considerably
improved this work.
[10]
[11]
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L. Dostál, R. Jambor, A. Ru˚zicˇka, J. Holecˇek, Organometallics
2008, 27, 2169–2171.
ˇ
[1] The NCN ligand has a long tradition in the field of both transi-
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Joint Committee on Powder Diffraction Standards, International
Centre of Diffraction Data, Swarthmore, PA.
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[2] a) L. Dostál, R. Jambor, A. Ru˚zicˇka, M. Erben, R. Jirásko, Z.
ˇ
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Cernosˇková, J. Holecˇek, Organometallics 2009, 28, 2633–2636;
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Received: July 8, 2010
Ru˚zicˇka, M. Erben, R. Jirásko, L. Dostál, Organometallics
ˇ
2009, 28, 5522–5528; c) L. Dostál, R. Jambor, A. Ru˚zicˇka, R.
Jirásko, V. Locharˇ, L. Benesˇ, F. de Proft, Inorg. Chem. 2009,
ˇ
Published Online: October 12, 2010
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 5222–5230