Regiospecific calcium-mediated intermolecular hydrophosphanylation of butadiynes with diphenylphosphane oxide

Article abstract of DOI:10.1002/ejic.201201138

Calcium-mediated hydrophosphanylation of diphenyl- and di(tert-butyl) butadiyne (2,2,7,7-tetramethyl-3,5-octadiyne) with diphenylphosphane oxide yields 1,4-diphenyl-1,3-butadiene-2,3-bis(diphenylphosphane oxide) and 2,2,7,7-tetramethyl-4-octyne-3,6-bis(di

Full text of DOI:10.1002/ejic.201201138

SHORT COMMUNICATION
DOI: 10.1002/ejic.201201138
Regiospecific Calcium-Mediated Intermolecular Hydrophosphanylation of
Butadiynes with Diphenylphosphane Oxide
Tareq M. A. Al-Shboul,[a] Helmar Görls,[a] Sven Krieck,[a] and Matthias Westerhausen*[a]
Keywords: Calcium / Phosphorus / Alkynes / Regioselectivity
Calcium-mediated hydrophosphanylation of diphenyl- and
di(tert-butyl)butadiyne (2,2,7,7-tetramethyl-3,5-octadiyne)
with diphenylphosphane oxide yields 1,4-diphenyl-1,3-buta-
diene-2,3-bis(diphenylphosphane oxide) and 2,2,7,7-tetra-
methyl-4-octyne-3,6-bis(diphenylphosphane oxide), respec-
tively. Alternatively, 1,4-diphenylphosphanyl-substituted
1,4-butadienes are quantitatively oxidized by H2O2 to the
corresponding 1,3-butadiene-1,4-bis(diphenylphosphane ox-
ides).
The dominance of electrostatic forces in complexes with
highly electropositive metals complicates stereochemical
control of catalysis, and hence, a ligand system has to be
designed that allows it to govern the catalytic cycle. The
hydrophosphanylation of substituted butadiynes with di-
phenylphosphane in the presence of catalytic amounts of
easily accessible [(thf)4Ca(PPh2)2] (which can crystallize as
trans[6] and cis isomers[7]) yielded isomeric mixtures of dou-
bly hydrophosphanylated products.[8] Replacement of one
diphenylphosphanide anion by a bulky substituent im-
proved the stereocontrol of the catalytic process; however,
the increased stereocontrol was accompanied by reduced
activity of the calcium-based catalyst. Crimmin et al. used
sterically demanding bidentate β-diketiminate anions to
protect the reactive calcium-based catalytic site in the hy-
drophosphanylation of carbodiimides,[9] alkenes, and al-
kynes.[10] Very recently, Hu and Cui developed a related an-
ionic ligand with enhanced denticity that also gave an effec-
tive calcium-based catalyst for the hydrophosphanylation of
alkenes and alkynes.[11] Control of stereochemistry by bulky
groups requires longer reaction times and harsher reaction
conditions such as higher reaction temperatures and higher
catalyst loadings.
Lack of control resulting from the use of catalytic
amounts of [(thf)4Ca(PPh2)2] is caused by the poor stability
of the phosphane adducts of calcium complexes[12] that
form as intermediates during this reaction. Contrary to this
observation, phosphane oxides yield stable compounds, and
quantum chemical calculations verified that OPR3 are
rather strong Lewis bases that can be used as a substitute
for water in a Ca2+ environment and that the formed inter-
mediates can be isolated and characterized.[12–14] Therefore,
hydrophosphanylation of butadiynes with phosphane ox-
ides offers the possibility to maintain close contact between
the calcium-based catalyst and the monophosphanylated in-
termediate that is essential for regiocontrolled catalysis. An
Introduction
Metal-mediated addition of H–P bonds (hydrophos-
phanylation) to alkenes and alkynes represents an atom
economic procedure for the synthesis of alkyl- or vinyl-sub-
stituted phosphanes. Depending on the metal, various
mechanistic steps are commonly discussed for transition-
metal-mediated hydrophosphanylation, including oxidative
addition of H–E to the metal, activation of the alkenes and
alkynes by side-on coordination (π complex formation),
and reductive elimination.[1] However, in s-block chemistry,
the oxidation state of the metal does not change and feas-
ible reaction steps involve insertion, metalation, cycload-
dition, and ligand redistribution. Even though a butadiyne
complex of decamethylcalcocene is known,[2] the bonding
parameters are similar to values of an uncoordinated mole-
cule, and CϵC activation cannot be assumed because of
the lack of charge back donation. The heavier alkaline earth
metals show an oxidation state of +2, low electronegativity,
mild Lewis acidity, and an intermediate position between
alkali metals (ionic bonds, salt-like behavior) and elements
of the scandium group (d-orbital participation,[3] catalytic
activity). In addition, calcium is naturally abundant over
the world, easily available, inexpensive, and nontoxic.
Therefore, this metal represents an extremely attractive
metal for catalytic purposes,[4] and two excellent reviews
summarize the early successes resulting from its use.[5] In
addition, these environmental arguments support calcium-
based catalysis and also the necessity to substitute expens-
ive and rare transition metals and lanthanoids in catalytic
applications.
[a] Institut für Anorganische und Analytische Chemie,
Friedrich-Schiller-Universität Jena,
Humboldtstraße 8, 07743 Jena, Germany
E-mail: m.we@uni-jena.de
Homepage: www.lsac1.uni-jena.de
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T. M. A. Al-Shboul, H. Görls, S. Krieck, M. Westerhausen
SHORT COMMUNICATION
essential step in the catalytic cycle was already verified,
namely, the ability of [(thf)4Ca(PPh2)2] to deprotonate di-
phenylphosphane oxide to yield the phosphinite [(thf)4Ca(-
OPPh2)2] with the calcium atoms bound to the oxygen
atoms.[15]
Results and Discussion
In a typical procedure, to a solution of the doubly substi-
tuted butadiyne and a twofold amount of diphenylphos-
phane oxide, HP(O)Ph2, dissolved in THF was added
5 mol-% of the catalyst [(thf)4Ca(PPh2)2] at –78 °C
(Scheme 1, top). After warming to room temperature, the
solution was stirred for several hours. Common workup
procedures gave phosphane oxides 1 and 2 in good yields.
Formation of 1 proceeds through twofold vicinal cis-ad-
dition of the P–H bonds to the alkyne moieties, whereas 2
resembles the product of a twofold 1,4-addition of the P–H
bonds to the butadiyne unit. In both products, the substitu-
tion pattern is strikingly different from that obtained in the
calcium-mediated hydrophosphanylation of diphenylbut-
adiyne and 2,2,7,7-tetramethylocta-3,5-diyne with diphenyl-
phosphane, which yields primarily 1,4-diphenyl-1,4-bis(di-
phenylphosphanyl)buta-1,3-diene and 2,2,7,7-tetramethyl-
Scheme 2. Oxidation of 1,4-disubstituted 1,4-bis(diphenylphos-
phanyl)butadienes with hydrogen peroxide to yield corresponding
phosphane oxides 3.
ures 1, 2, and 3.[16] Bisphosphoryl-1,3-butadienes 1 and 2
show substitution patterns that could not be achieved by
the calcium-mediated hydrophosphanylation of butadiynes
with HPPh2. The butadiene backbone of 1 shows a typical
unconjugated system with C–C double [134.6(4) pm] and
single bonds [149.0(4) pm]. The P–C bonds to the butadiene
unit [av. 182.6(3) pm] are lengthened compared to the P–
CPh bonds [av. 180.5(3) pm] to the phenyl groups. As ex-
pected, the P=O moiety [148.6(2) pm] shows double-bond
character, and the bonding situation is in agreement with
earlier discussions.[20] An unexpected structure is also real-
ized in centrosymmetric derivative 2 with a central alkyne
fragment [CϵC 119.2(4) pm], which was inert under these
reaction conditions. As a result of the fact that the phos-
phorus atom is bound to an alkyl group (sp3 hybridization
at the carbon atom), as expected, even greater elongation is
observed [P1–C1 184.2(2) pm], whereas the P=O
3,6-bis(diphenylphosphanyl)octa-3,4-diene,
respectively
(Scheme 1, bottom).[8] In contrast, oxidation of 1,4-disub-
stituted 1,4-bis(diphenylphosphanyl)buta-1,3-dienes with
hydrogen peroxide offers phosphane oxides 3 with a dif-
ferent substitution pattern according to Scheme 2.
Figure 1. Molecular structure and numbering scheme of 1. Ellip-
soids are drawn at the 40% probability level, H atoms are shown
with arbitrary radii. The asymmetric unit contains two molecules
that are distinguished by the letters “A” and “B”. Selected bond
lengths of molecule A [molecule B] (pm): P1–O1 148.6(2) [147.7(2)],
P1–C2 182.1(3) [183.0(3)], P1–C5 180.8(3) [181.6(3)], P1–C11
180.2(3) [180.1(3)], P2–O2 147.9(2) [148.0(2)], P2–C3 183.0(3)
[183.0(3)], P2–C23 180.1(3) [180.5(3)], P2–C29 180.8(3) [182.3(3)],
C1–C2 134.6(4) [134.0(4)], C2–C3 149.0(4) [149.5(4)], C3–C4
Scheme 1. Synthesis of 1 and 2 by calcium-mediated hydrophos-
phanylation of substituted butadiynes with diphenylphosphane ox-
ide (top) and diphenylphosphane (bottom).
These phosphane oxides are poorly soluble in THF and
precipitated from concentrated solutions or were crys-
tallized from methanol solutions. The molecular structures
and numbering scheme of 1, 2, and 3b are shown in Fig- 134.5(4) [134.6(4)].
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Eur. J. Inorg. Chem. 2012, 5451–5455

Regiospecific Ca-Mediated Intermolecular Hydrophosphanylation
[149.1(2) pm] and P–CPh bonds [av. 181.5(2) pm] adopt
characteristic values. Derivative 3b shows comparable
bonding parameters [P=O 148.9(2) pm, C=C 134.6(3) pm,
C–C 145.7(3) pm], although the differences in the P–C
bonds is rather small [av. P–Cdiene 180.6(2) pm, P–CPh
179.8(3) pm]. The structural parameters of 3a [P=O
148.6(2) pm, C=C 133.8(4) pm, C–C 145.9(5) pm; P–Cdiene
180.7(3) pm, av. P–CPh 180.4(3) pm] and 3c [P=O
148.6(1) pm, C=C 135.0(2) pm, C–C 146.1(4) pm; P–Cdiene
181.1(2) pm, av. P–CPh 180.8(2) pm] are very similar and
unexceptional.
Conclusions
Hydrophosphanylation of phenyl- and tert-butyl-substi-
tuted butadiynes with diphenylphosphane oxide leads to the
formation of 1,4-diphenyl-2,3-bis(diphenylphosphoryl)-
buta-1,3-diene (1) and 2,2,7,7-tetramethyl-3,6-bis(diphenyl-
phosphoryl)-4-octyne (2), respectively, which were not ac-
cessible by employing diphenylphosphane in this calcium-
mediated H–P addition to CϵC bonds. In addition, this
reaction provides effective regiocontrol of the catalyst be-
cause a rather strong Ca–O Lewis acid–base interaction of
the calcium catalyst requires that the alkaline earth metal
cation stays in close vicinity of the reactive C–C multiple
bonds. Neither phosphanes nor alkynes are strong bases,
and a significantly weaker interaction between the metal
and the substrates or intermediates during the catalytic hy-
drophosphanylation with phosphanes allows dissociation
and reorganization processes. Intermolecular calcium-medi-
ated hydrophosphanylation of substituted butadiynes with
phosphane oxides adds a competitive method for the regios-
pecific addition of P–H bonds to alkyne moieties in ad-
dition to the many versatile procedures already known with
other metals.[21] Theoretical calculations on a Pd-based cat-
alyst very recently verified the importance of the preorien-
tation of the phosphorus-containing groups [HPR2, HP(O)-
R2, HP(O)(OR)2] to achieve regiospecific addition of P–H
bonds to alkynes.[22]
Experimental Section
Figure 2. Molecular structure and numbering scheme of 2. Ellip-
soids are drawn at the 40% probability level, H atoms are shown
with arbitrary radii. Symmetry-related atoms (–x, –y + 1, –z + 1)
are marked with the letter “A”. Selected bond lengths (pm): P1–O1
149.1(2), P1–C1 184.2(2), P1–C7 180.9(2), P1–C13 181.8(2), C1–
C2 147.5(3), C2–C3 156.8(3), C2–C2A 119.2(4).
General: The [(thf)4Ca(PPh2)2] catalyst is air- and moisture-sensi-
tive and has to be handled under strictly anaerobic conditions.[6]
1,4-Disubstituted 1,4-bis(diphenylphosphanyl)buta-1,3-dienes were
prepared according to literature procedures.[8]
1,4-Diphenyl-2,3-bis(diphenylphosphoryl)buta-1,3-diene (1): A solu-
tion of [(thf)4Ca(PPh2)2] (5 mol-%) dissolved in a few milliliters of
THF was added at –78 °C to a stirred solution of diphenylbut-
adiyne (0.80 g, 3.96 mmol) and HP(O)Ph2 (1.6 g, 7.91 mmol) in
THF (8 mL). The reaction mixture was warmed to room tempera-
ture and stirred overnight. The precipitate was collected and
washed with diethyl ether to obtain pure product 1 (1.97 g,
3.25 mmol, 82%). C40H32O2P2 (606.63): calcd. C 79.20, H 5.32;
found C 79.17, H 5.26. 1H NMR (400 MHz, 298 K, CDCl3, X-
parts of AAЈX-type resonances): δ = 7.14–7.46 (m, aryl), 7.50–7.61
(m, CH) ppm. 13C{1H} NMR (101 MHz, 298 K, CDCl3): δ = 128.0
(4 C), 128.3 (s, 8 C), 129.4 (s, 8 C), 130.4 (2 C), 131.4 (4 C), 132.1
(4 C), 132.6 (4 C), 132.8 (s, 2 C), 135.6 (2 C), 147.8 (2 C) ppm.
31P{1H} NMR (162 MHz, 298 K, CDCl ): δ = 29.8 (s) ppm. IR: ν
˜
3
= 1605 (w), 1588 (m), 1567 (m), 1377 (m), 1353 (w), 1309 (w), 1191
(vs), 1160 (s), 1116 (s), 1100 (m), 1069 (w), 1032 (m), 1025 (m), 998
(m), 920 (w), 893 (m), 848 (w), 813 (w), 753 (s), 722 (vs), 691 (vs),
598 (s), 582 (vs), 537 (m), 520 (w), 506 (m), 474 (w) cm–1. MS
(DEI): m/z (%) = 606 (9) [M]+, 405 (100) [M – OPPh2]+, 201 (15)
[OPPh2]+.
Figure 3. Molecular structure and numbering scheme of 3b. Ellip-
soids are drawn at the 40% probability level, H atoms are shown
with arbitrary radii. Selected bond lengths (pm): P1–O1 148.9(2),
P1–C1 180.7(2), P1–C17 179.1(2), P1–C23 179.1(2), P2–O2
148.3(2), P2–C4 180.5(2), P2–C29 181.0(2), P2–C35 179.4(2), C1–
C2 134.9(3), C1–C5 148.9(3), C2–C3 145.7(3), C3–C4 134.3(3), C4–
C11 148.5(3).
2,2,7,7-Tetramethyl-3,6-bis(diphenylphosphoryl)-4-octyne (2):
A
solution of [(thf)4Ca(PPh2)2] (5 mol-%) dissolved in a few milliliters
of THF was added at –78 °C to a stirred solution of 3,5-bis(diphen-
ylphosphanyl)-3,5-octadiyne (0.15 g, 1.92 mmol) and HP(O)Ph2
(0.78 g, 3.86 mmol) in THF (6 mL). The reaction mixture was
warmed to room temperature and stirred overnight. The precipitate
Eur. J. Inorg. Chem. 2012, 5451–5455
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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5453

T. M. A. Al-Shboul, H. Görls, S. Krieck, M. Westerhausen
SHORT COMMUNICATION
was collected and washed with diethyl ether to obtain pure product
graphic data for this paper. These data can be obtained free of
2 (0.92 g, 1.62 mmol, 84%). C36H40O2P2 (566.65): calcd. C 76.31, H charge from The Cambridge Crystallographic Data Centre via
7.12; found C 76.23, H 7.08. 1H NMR (200 MHz, 298 K, CDCl3): δ
www.ccdc.cam.ac.uk/data_request/cif.
2
= 0.74 (s, 18 H, tBu), 3.25 (d, JHP = 9.8 Hz, 2 H), 7.25–7.88 (m,
aryl) ppm. 31P{1H} NMR (162 MHz, 298 K, CDCl3): δ = 32.6
Acknowledgments
(s) ppm. IR: ν = 1673 (w), 1640 (w), 1591 (w), 1396 (w), 1376 (m),
˜
1366 (m), 1340 (w), 1317 (w), 1239 (w), 1219 (w), 1188 (vs), 1160
(s), 1117 (s), 1102 (m), 1070 (m), 1038 (m), 1021 (w), 998 (w), 928
(w), 860 (w), 798 (w), 745 (m), 724 (s), 696 (vs), 584 (s), 542 (s),
530 (vs), 470 (w) cm–1. MS (DEI): m/z (%) = 566 (3) [M]+, 509 (20)
[M – tBu]+, 435 (33), 295 (17), 201 (100) [OPPh2]+, 77 (35) [Ph]+.
S. K. gratefully acknowledges the financial support of the Fonds
der Chemischen Industrie (VCI/FCI, Frankfurt a.M./Germany).
We also thank the German Research Foundation (DFG, Bonn/
Germany) for financial support.
General Procedure for the Synthesis of 1,4-Disubstituted 1,4-Bis(di-
phenylphosphoryl)buta-1,3-dienes (3): To a solution of the 1,4-di-
substituted 1,4-bis(diphenylphosphanyl)buta-1,3-diene (0.17 μmol)
dissolved in THF (8 mL) was added H2O2 (30%, 0.036 mL,
0.34 μmol) dropwise with a syringe at 0 °C. Then, the reaction mix-
ture was stirred for 1 h at room temperature. After reduction of the
volume to half of the original volume, methanol (4 mL) was added.
Within 6 d, colorless crystals of 3 were obtained at room tempera-
ture (approx. 90% yield).
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3a: M.p. 213–215 °C. MS (EI): m/z (%) = 482 (100) [M]+, 281 (40)
[M – OPPh2]+, 201 (60) [OPPh2]+. 1H NMR (200.13 MHz, CDCl3):
3
3
4
δ = 7.13 (AAЈXXЈ type, JAAЈ = 11.2 Hz, JAX = 18.8 Hz, JAXЈ
=
1.3 Hz, JXXЈ = 0 Hz, CH), 7.4–7.7 (phenyl) ppm. 13C{1H} NMR
(50.328 MHz, CDCl3): δ = 128.5 (8 C, JCP = 4.6 Hz), 128.9 (4 C,
JCP = 6.0 Hz), 129.5 (4 C), 14.1 (2 C), 132.1 (8 C, JCP = 22.4 Hz),
135.1 (2 C, JCP = 2.9 Hz), 136.9 (2 C) ppm. 31P NMR (81.01 MHz,
5
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CDCl ): δ = 36.2 ppm. IR (KBr): ν = 1626 (m), 1589 (m), 1573
˜
3
(w), 1461 (vs), 1440 (vs), 1378 (vs), 1312 (m), 1244 (w), 1169 (vs),
1118 (vs), 1093 (w), 1071 (m), 1026 (m), 996 (s), 966 (s), 907 (w),
861 (w), 752 (s), 723 (vs), 697 (vs), 662 (s), 621 (w), 590 (w), 545
(vs), 504 (w) cm–1. C30H28O2P2 (482.49): calcd. C 74.68, H 5.85;
found C 74.44, H 5.83.
3b: M.p. 276–279 °C. MS (EI): m/z (%) = 606 (1) [M]+, 405 (100)
[M – OPPh2]+, 201 (20) [OPPh2]+. 1H NMR (200.13 MHz, CDCl3):
3
3
4
δ = 6.73 (AAЈXXЈ type, JAAЈ = 10.9 Hz, JAX = 19.2 Hz, JAXЈ
=
1.1 Hz, JXXЈ = 0 Hz, CH), 7.2–7.5 (phenyl) ppm. 13C{1H} NMR
(50.328 MHz, CDCl3): δ = 128.0 (4 C), 128.3 (4 C), 128.4 (2 C),
129.5 (8 C, JCP = 20 Hz), 131.9 (8 C, JCP = 9.4 Hz), 134.1 (4 C,
JCP = 8.1 Hz), 137.8 (4 C), 138.2 (2 C, JCP = 14.3 Hz), 141.9 (2 C),
143.6 (2 C) ppm. 31P NMR (81.01 MHz, CDCl3): δ = 33.6 ppm.
5
IR (KBr): ν = 1968 (w), 1901 (w), 1825 (w), 1590 (m), 1574 (w),
˜
1552 (w), 1487 (s), 1437 (vs), 1311 (m), 1279 (w), 1192 (vs), 1117
(vs), 1100 (s), 1072 (m), 1029 (m), 998 (m), 935 (w), 900 (s), 851
(w), 768 (m), 752 (m), 724 (vs), 701 (vs), 631 (w), 617 (w), 603 (s),
584 (w), 566 (m), 548 (vs), 507 (s) cm–1. C40H32O2P2 (606.63): calcd.
C 79.20, H 5.32; found C 79.10, H 5.13.
3c: M.p. 182–185 °C. MS (EI): m/z (%) = 598 (1) [M]+, 397 (100)
[M – OPPh2]+, 201 (20) [OPPh2]+. 1H NMR (200.13 MHz, CDCl3):
3
3
4
δ = 7.03 (AAЈXXЈ type, JAAЈ = 11.4 Hz, JAX = 30.2 Hz, JAXЈ
=
1.1 Hz, JXXЈ = 0 Hz, CH), 7.4–7.7 (phenyl) ppm. 13C{1H} NMR
(50.328 MHz, CDCl3): δ = 128.7 (8 C, JCP = 12.3 Hz), 131.7 (8 C,
JCP = 7.3 Hz), 133.4 (4 C), 147.4 (4 C), 148.7 (2 C), 151.3 (2 C,
JCP = 29.7 Hz), 0.7 (2 C) ppm. 31P NMR (81.01 MHz, CDCl3): δ
5
= 40.8 ppm. IR (KBr): ν = 1963 (w), 1900 (w), 1821 (w), 1711 (w),
˜
1590 (m), 1483 (s), 1437 (vs), 1407 (w), 1309 (m), 1250 (vs), 1189
(vs), 1118 (vs), 1100 (s), 1070 (m), 1026 (m), 998 (m), 898 (s), 875
(m), 842 (vs), 746 (s), 722 (s), 696 (vs), 635 (s), 617 (w), 570 (s), 538
(vs) cm–1. C34H40O2P2Si2 (598.80): calcd. C 68.20, H 6.73; found C
67.24.10, H 6.59.
[15] T. M. A. Al-Shboul, G. Volland, H. Görls, S. Krieck, M. West-
erhausen, Inorg. Chem. 2012, 51, 7903–7912.
[16] The intensity data were collected with a Nonius KappaCCD
diffractometer by using graphite-monochromated Mo-Kα radi-
ation. Data were corrected for Lorentz and polarization effects,
CCDC-892427 (for 1), -892428 (for 2), -892429 (for 3a), -892430
(for 3b), and -892431 (for 3c) contain the supplementary crystallo-
5454
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 5451–5455

Regiospecific Ca-Mediated Intermolecular Hydrophosphanylation
but not for absorption.[17,18] The structure was solved by direct
methods (SHELXS[19]) and refined by full-matrix least-squares
group P21/c, a = 19.0991(5) Å, b = 9.3722(3) Å, c =
19.0991(5) Å, β = 104.750(2)°, V = 3306.09(16) Å3, T = –90 °C,
Z = 4, ρcalcd. = 1.283 gcm–3, μ(Mo-Kα) = 1.71 cm–1, F(000)=
1344, 21777 reflections in h(–24/19), k(–11/12), l(–24/23), mea-
techniques against Fo (SHELXL-97[19]). The hydrogen atoms
2
of 2 and 3c were located by difference Fourier synthesis and
refined isotropically.[19] All other hydrogen atoms were in-
cluded at calculated positions with fixed thermal parameters.
XP (SIEMENS Analytical X-ray Instruments, Inc.) was used
for structure representations. Crystal Data for 1:
sured in the range 2.56 Յ θ Յ 27.48°, completeness θmax
=
99%, 7513 independent reflections, Rint = 0.0578, 5054 reflec-
tions with Fo Ͼ 4σ(Fo), 432 parameters, 0 restraints, R1(obs) =
0.0557, wR2(obs) = 0.1355, R1(all) = 0.0956, wR2(all) = 0.1548,
GOOF = 1.015, largest difference peak and hole: 0.595/–
C40H32O2P2·0.5H2O, 615.60 gmol–1, colorless prism, size
0.05ϫ0.05ϫ0.05 mm3, triclinic, space group P1,
12.1182(4) Å,
a
=
=
0.577 eÅ–3.
Crystal
Data
for
3c:
C34H40O2P2Si2,
¯
b = 15.3992(7) Å, c = 17.8743(7) Å, α
598.78 gmol–1, colorless prism, size 0.05ϫ0.05ϫ0.05 mm3,
97.507(2)°, β = 96.096(2)°, γ = 105.339(2)°, V = 3154.4(2) Å3, T
= –90 °C, Z = 4, ρcalcd. = 1.296 gcm–3, μ(Mo-Kα) = 1.75 cm–1,
F(000)= 1292, 22426 reflections in h(–15/15), k(–19/19), l(–23/
23), measured in the range 1.96 Յ θ Յ 27.50°, completeness
θmax = 99.4%, 14397 independent reflections, Rint = 0.0564,
7307 reflections with Fo Ͼ 4σ(Fo), 818 parameters, 0 restraints,
R1(obs) = 0.0647, wR2(obs) = 0.1221, R1(all) = 0.1601,
wR2(all) = 0.1534, GOOF = 0.989, largest difference peak and
hole: 0.420/–0.396 eÅ–3. Crystal Data for 2: C36H40O2P2,
566.62 gmol–1, colorless prism, size 0.06ϫ0.05ϫ0.04 mm3, tri-
monoclinic, space group P21/n,
11.0230(4) Å, 16.4554(7) Å,
a
β
=
=
9.0911(4) Å,
100.455(2)°,
b
V
=
=
c
=
1621.64(12) Å3, T = –90 °C, Z = 2, ρcalcd. = 1.226 gcm–3, μ(Mo-
Kα) = 2.37 cm–1, F(000)= 636, 10995 reflections in h(–11/11),
k(–13/14), l(–20/21), measured in the range 2.93 Յ θ Յ 27.48°,
completeness θmax = 99.8%, 3721 independent reflections, Rint
= 0.0505, 2580 reflections with Fo Ͼ 4σ(Fo), 261 parameters,
0 restraints, R1(obs) = 0.0421, wR2(obs) = 0.0978, R1(all) =
0.0759, wR2(all) = 0.1120, GOOF = 0.960, largest difference
peak and hole: 0.242/–0.366 eÅ–3.
¯
clinic, space group P1, a = 5.7988(5) Å, b = 9.9701(6) Å, c =
[17] B. V. Nonius, COLLECT: Data Collection Software, Nether-
lands, 1998.
13.7726(12) Å, α = 91.230(4)°, β = 101.726(3)°, γ = 103.452(5)°,
V = 756.27(10) Å3, T = –140 °C, Z = 1, ρcalcd. = 1.244 gcm–3, [18] Z. Otwinowski, W. Minor, “Processing of X-ray Diffraction
μ(Mo-Kα) = 1.75 cm–1, F(000)= 302, 4591 reflections in h(–7/5),
k(–12/12), l(–13/17), measured in the range 2.50 Յ θ Յ 27.49°,
completeness θmax = 95.5%, 3322 independent reflections, Rint
= 0.0212, 2907 reflections with Fo Ͼ 4σ(Fo), 261 parameters,
0 restraints, R1(obs) = 0.0549, wR2(obs) = 0.1076, R1(all) =
0.0664, wR2(all) = 0.1151, GOOF = 1.159, largest difference
peak and hole: 0.374/–0.301 eÅ–3. Crystal Data for 3a:
C30H28O2P2·2CH2Cl2, 652.32 gmol–1, colorless prism, size
0.06ϫ0.06ϫ0.04 mm3, monoclinic, space group P21/n, a =
Data Collected in Oscillation Mode” in Methods in Enzy-
mology Vol. 276: Macromolecular Crystallography, Part A
(Eds.: C. W. Carter, R. M. Sweet), Academic Press, San Diego,
1997, pp. 307–326.
[19] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
[20] D. G. Gilheany, Chem. Rev. 1994, 94, 1339–1374.
[21] See, for example, the following recent reviews: a) S. Lühr, J.
Holz, A. Börner, ChemCatChem 2011, 3, 1708–1730; b) D. Juli-
enne, O. Delacroix, A.-C. Gaumont, Curr. Org. Chem. 2010,
14, 457–482; c) Ł. Albrecht, A. Albrecht, H. Krawczyk, K. A.
Jørgensen, Chem. Eur. J. 2010, 16, 28–48; d) D. S. Glueck,
Chem. Eur. J. 2008, 14, 7108–7117; L. Coudray, J.-L. Montch-
amp, Eur. J. Inorg. Chem. 2008, 3601–3613; e) L. Mei, Lett.
Org. Chem. 2008, 5, 174–190; f) J.-L. Montchamp, J. Or-
ganomet. Chem. 2005, 690, 2388–2406; g) C. Baillie, J. Xiao,
Curr. Org. Chem. 2003, 7, 477–514.
8.5553(4) Å,
b
=
16.2259(8) Å,
c
=
12.3938(3) Å,
β
=
=
109.850(2)°, V = 1618.25(12) Å3, T = –90 °C, Z = 2, ρcalcd.
1.339 gcm–3, μ(Mo-Kα) = 4.93 cm–1, F(000)= 676, 11284 reflec-
tions in h(–11/10), k(–20/21), l(–16/15), measured in the range
2.15 Յ θ Յ 27.45°, completeness θmax = 99.5%, 3680 indepen-
dent reflections, Rint = 0.0325, 2909 reflections with Fo
Ͼ
4σ(Fo), 182 parameters, restraints, R1(obs) 0.0682,
0
=
wR2(obs) = 0.1865, R1(all) = 0.0848, wR2(all) = 0.2013, GOOF
= 1.006, largest difference peak and hole: 0.885/–0.858 eÅ–3.
Crystal Data for 3b: C40H32O2P2·CH4O, 638.64 gmol–1, color-
less prism, size 0.06ϫ0.06ϫ0.05 mm3, monoclinic, space
[22] V. P. Ananikov, A. V. Makarov, I. P. Beletskaya, Chem. Eur. J.
2011, 17, 12623–12630.
Received: September 24, 2012
Published Online: October 17, 2012
Eur. J. Inorg. Chem. 2012, 5451–5455
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5455