Synthetic and structural studies of PdII and PtII complexes with quincorine and quincoridine derivatives

Article abstract of DOI:10.1002/ejic.200300557

A series of Pd^II-quincorine and -quincoridine complexes in which the ligands are coordinated through N,O-donor atoms have been synthesised, and their structural features determined by X-ray crystallography. Additionally, new chiral tetradentate N,P-ligands containing two quinuclidine cores bridged through a cis-enediyne fragment have been obtained. The different coordinating properties of the new ligands, which contain two soft phosphorus and two hard nitrogen donors, to Pd^II and Pt^II are emphasised. Several typical complexes were structurally characterised by X-ray crystallography. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Full text of DOI:10.1002/ejic.200300557

FULL PAPER
Synthetic and Structural Studies of PdII and PtII Complexes with Quincorine
and Quincoridine Derivatives
Manfred Fild,[a] Carsten Thöne,*[a] and Stefania Tötös[a]
Keywords: N,P ligands / Heterocycles / Palladium / Platinum / Bioinorganic chemistry
A series of PdII-quincorine and -quincoridine complexes in
which the ligands are coordinated through N,O-donor atoms
gands, which contain two soft phosphorus and two hard ni-
trogen donors, to PdII and PtII are emphasised. Several typical
have been synthesised, and their structural features deter- complexes were structurally characterised by X-ray crystallo-
mined by X-ray crystallography. Additionally, new chiral
graphy.
tetradentate N,P-ligands containing two quinuclidine cores
bridged through a cis-enediyne fragment have been ob- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
tained. The different coordinating properties of the new li-
Germany, 2004)
Introduction
Additionally, bidentate N,P-ligands have acquired a
growing importance in the development of coordination
chemistry and asymmetric catalysis.[6] A remarkable num-
ber of aminophosphane, -phosphite, -phosphonite and
-phosphinite ligands have been developed and their com-
plexes used for asymmetric catalytic reactions, such as
cross-coupling, hydroformylation and hydrogenation.[7Ϫ9]
Beck et al. reported the first N,O-chelate complexes of
cinchonidine and cinchonine, but only a few metal com-
plexes of cinchona alkaloids have been described.[10] Quin-
coridine-based aminophosphite ligands and their RhI and
PdII complexes have also been reported by Gavrilov and co-
workers.[11] Recently, Lemaire et al. have developed a new
family of N,P-ligands derived from quincorine (QCI) and
quincoridine (QCD) with applications in hydroformylation,
asymmetric hydrosilylation and asymmetric Grignard cross-
coupling reactions.[12]
The development of asymmetric catalysis using chiral or-
ganic compounds or chiral metal complexes has induced an
increased interest in the synthesis of new optically active
ligands.[1,2] In this context cinchona alkaloids, such as quin-
ine and quinidine and their derivatives, readily available in
both pseudo-enantiomeric forms, play an important role
and are extensively used. Among asymmetric synthetic
procedures in organic chemistry, one of the best known is
the asymmetric dihydroxylation of olefins using various
cinchona alkaloid derivatives as chiral monodentate amine
ligands for OsO4 as developed by Sharpless.[3] The mecha-
nism of this reaction was also extensively analysed by
Corey, and the most efficient ligands for promoting face-
selective dihydroxylation of olefins were found to be bis-
cinchona alkaloids such as the (DHQD)2PHAL system
(Figure 1).[3Ϫ5]
The chirality, in combination with the donor properties of
QCI and QCD, should provide a useful ligand system for
catalytic processes. QCI and QCD contain four stereogenic
centres each, including the N-chiral 1S-configured bridgehead
and also possess three potential donor sites: the OH group,
a tertiary N-atom and an olefinic CϭC bond (Figure 2).
Figure 1. (DHQD)2PHAL, a bis-cinchona alkaloid
[a]
Institut für Anorganische und Analytische Chemie der
Technischen Universität,
Figure 2. Atom numbering scheme and stereocentres in quincorine
(QCI) and quincoridine (QCD)
Hagenring 30, 38106 Braunschweig, Germany
Eur. J. Inorg. Chem. 2004, 749Ϫ761
DOI: 10.1002/ejic.200300557
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749

M. Fild, C. Thöne, S. Tötös
FULL PAPER
In the present work we report on new N,O-chelate and
Reactions of two equivalents of the ligands 1Ϫ4 with one
bis-N,O-chelate complexes of PdII with QCI and QCD and equivalent of the chloro-bridged complex [(Ph3P)(Cl)Pd(µ-
their corresponding saturated derivatives. New chiral Cl)2Pd(Cl)(PPh3)] in the presence of NaOMe in CH3OH/
aminophosphinites, containing two quinuclidine cores CH2Cl2 gave the corresponding five-membered ring chelate
bridged through a cis enediyne fragment, are developed and complexes 5Ϫ8 (Scheme 2).
their different coordination modes are described.
All of the complexes 5Ϫ8 gave the expected fragmen-
tation patterns in their positive FAB mass spectra. In the
31P{1H} NMR spectra of 5Ϫ8 all compounds display two
singlets around δ ϭ 26 (high intensity) and 23 ppm (low
Results and Discussion
N,O-Chelate Complexes
In the course of this research program directed toward
the synthesis and characterisation of new metal complexes,
we have used QCI [(2S,4S,5R)-2-hydroxymethyl-5-vinyl-2-
quinuclidine] (1) and QCD [(2R,4S,5R)-2-hydroxymethyl-5-
vinyl-2-quinuclidine] (2) as ligands. The corresponding satu-
rated derivatives [(2S,4S,5R)-5-ethyl-2-hydroxymethyl-2-
quinuclidine] (3) and [(2R,4S,5R)-5-ethyl-2-hydroxymethyl-
2-quinuclidine] (4) were prepared efficiently by hydrogen-
ation, according to
a
known literature procedure
(Scheme 1).[13]
Figure 3. The molecular structure of 7; H atoms omitted for clarity;
˚
ellipsoids at 50% probability level; selected bond lengths [A] and
angles [°]: Pd1ϪP1 2.2480(6), Pd1ϪCl1 2.3020(6), Pd1ϪO1
1.9986(16), Pd1ϪN1 2.1043, O1ϪC8 1.407(3), N1ϪC1 1.496(3),
N1ϪC5 1.495(3), N1ϪC6 1.494(3), C(aliph.)ϪC(aliph.)
1.508(3)Ϫ1.549(3); O1ϪPd1ϪN1 84.69(7), N1ϪPd1ϪCl1 92.17(5),
Cl1ϪPd1ϪP1 95.99(2), P1ϪPd1ϪO1 87.08(5), C8ϪO1ϪPd1
108.87(13), O1ϪC8ϪC1 110.03(17), C8ϪC1ϪC2 115.78(18),
C8ϪC1ϪN1 108.54(17), N1ϪC1ϪC2 109.90(17), C1ϪN1ϪC5
107.78(17), C1ϪN1ϪC6 110.55(17), C5ϪN1ϪC6 108.38(17),
C3ϪC4ϪC5 107.86(18), C3ϪC4ϪC9 112.84(19), C5ϪC4ϪC9
112.99(18)
Scheme 1. The synthesis of dihydro-QCI (3) and dihydro-QCD (4)
Figure 4. The molecular structure of 8; H atoms omitted for clarity;
˚
ellipsoids at 50% probability level; selected bond lengths [A] and
angles [°]: Pd1ϪP1 2.2470(3), Pd1ϪCl1 2.3082(3), Pd1ϪO1
2.0036(8), Pd1ϪN1 2.1101(9), O1ϪC8 1.4034(15), N1ϪC1
1.5103(14),
N1ϪC5
1.4967(15),
N1ϪC6
1.4940(15),
O1ϪPd1ϪN1
C(aliph.)ϪC(aliph.)
1.5093(17)Ϫ1.5504(16);
85.27(4), N1ϪPd1ϪCl1 91.56(3), Cl1ϪPd1ϪP1 97.409(11),
P1ϪPd1ϪO1 85.81(2), C8ϪO1ϪPd1 107.79(7), O1ϪC8ϪC1
110.96(10), C8ϪC1ϪC2 116.19(10), C8ϪC1ϪN1 108.42(9),
N1ϪC1ϪC2 109.30(10), C1ϪN1ϪC5 111.17(9), C1ϪN1ϪC6
106.98(9), C5ϪN1ϪC6 107.70(9), C3ϪC4ϪC5 106.62(10),
C3ϪC4ϪC9 113.44(10), C5ϪC4ϪC9 111.40(10)
Scheme 2. The synthesis of phosphane PdII-QCI and -QCD com-
plexes
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PdII and PtII Complexes with Quincorine and Quincoridine Derivatives
FULL PAPER
intensity ഠ 5%). The signal with the high intensity was as-
signed to the trans-PϪMϪN isomer whereas the low inten-
sity signal corresponds to the cis-PϪMϪN isomer. The for-
mation of the five-membered chelate rings in 5Ϫ8 was also
1
confirmed in the H NMR spectra by the diastereotopicity
of the 9-H atoms: an upfield shift of ca. 0.5 ppm was ob-
served for one of them. The H-6 and H-7 atoms suffer a
small downfield shift probably because of interaction with
2
the dz orbital of the metal atom and the coordination of
the tertiary N-atom.
Deep yellow crystals of the QCI-PdII complex 7 and the
QCD-PdII complex 8, suitable for X-ray analysis, were ob-
tained from diethyl ether solutions by layering with hexanes.
Single-crystal X-ray structure determinations (Figure 3 and
4) proved that the trans-PϪMϪN isomers were formed as
the main products because of the steric demands of the
bulky ligands. The chirality at C-2 is retained in the com-
plexes. The coordination geometry around Pd is virtually
square planar in both cases (mean dev. in 7: 1.86 pm; 8:
Figure 5. The molecular structure of 9 in the crystal; non-water
hydrogens omitted for clarity; ellipsoids at 50% probability level;
˚
selected bond lengths [A] and angles [°]: Pd1ϪO1 1.9852(14),
Pd1ϪN1 2.0372(16), Pd1ϪO2 2.0006(14), Pd1ϪN2 2.0335(15),
O1ϪC17 1.401(2), O2ϪC27 1.400(2), N1ϪC20 1.502(2), N1ϪC24
1.484(2), N1ϪC25 1.487(2), N2ϪC10 1.501(2), N2ϪC14 1.478(2),
N2ϪC15 1.493(2), C13ϪC18 1.488(3), C18ϪC19 1.312(4),
C23ϪC28 1.499(3), C28ϪC29 1.312(3), C(aliph.)ϪC(aliph.)
1.508(3)Ϫ1.556(3), O1···H99a 1.79(5), O2···H98a 1.92(3);
O1ϪPd1ϪN1 94.10(6), N1ϪPd1ϪO2 85.24(6), O2ϪPd1ϪN2
95.32(6), N2ϪPd1ϪO1 85.49(6), C10ϪN2ϪPd1 103.67(11),
2.86 pm). The Pd atoms are incorporated into five-mem-
bered chelate rings. In the case of 7, the ring adopts a twist
conformation, and in 8 an envelope conformation, with C-
8 as the flap. The similarity in the bonding situation around
C14ϪN2ϪPd1
C20ϪN1ϪPd1
C25ϪN1ϪPd1
C24ϪC23ϪC28
115.40(11),
106.48(11),
104.60(11),
117.56(16),
C15ϪN2ϪPd1
C24ϪN1ϪPd1
C14ϪC13ϪC18
C13ϪC18ϪC19
108.82(11),
118.12(11),
115.26(18),
129.0(2),
C23ϪC28ϪC29 129.2(2)
Scheme 3. The synthesis of homoleptic PdII-QCI and -QCD complexes
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M. Fild, C. Thöne, S. Tötös
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Pd is also reflected in nearly identical bond lengths at Pd stereotopicity of the 9-H atoms. These exhibit a downfield
in both cases. They match the typically observed range for shift and an upfield shift associated with the different en-
PdϪP, PdϪCl and PdϪN bond lengths.
vironment obtained through the closure of the five-mem-
When one equivalent of trans-[PdCl2(PhCN)2] was re- bered chelate rings. The H-6 and H-7 atoms suffer a small
acted with two equivalents of 1Ϫ4 in the presence of Na- downfield shift, perhaps because of the coordination of the
2
OMe in methanol/dichloromethane, the bis-N,O-chelate tertiary N-atom to Pd and the interaction with the dz or-
complexes 9Ϫ12 were obtained in excellent yields (90%; bital of the metal.
Scheme 3).
Yellow crystals of 9 and 11 suitable for X-ray analysis
All of the compounds 9Ϫ12 show the expected fragmen- were obtained from Et2O by layering with hexanes. As
tation patterns and the molecular ions in their EI mass shown in Figure 5 and 6, the coordination geometry around
1
spectra. Again, the H NMR spectra confirmed the forma- Pd is square planar (mean dev. 9: 2.29 pm; 11: 4.73 pm),
tion of the spiro complexes 9Ϫ12 because of the dia- with N(1) and N(2) occupying the trans positions. Because
of the chelating ligands, Pd is in both cases the spiro atom
and therefore part of two five-membered ring systems that
display approximately envelope conformations, with the
quinuclidine-bound carbon atoms in the flap positions.
Figure 6. The molecular structure of 11 in the crystal; non-water
hydrogens omitted for clarity; ellipsoids at 50% probability level;
˚
selected bond lengths [A] and angles [°]: Pd1ϪO1 2.0054(10),
Pd1ϪN1 2.0475(11), Pd1ϪO2 2.0037(10), Pd1ϪN2 2.0522(11),
O1ϪC17 1.4048(17), O2ϪC27 1.4097(16), N1ϪC10 1.5149(17), Figure 7. The molecular structure of 18 in the crystal; H-atoms
N1ϪC14 1.4945(16), N1ϪC15 1.4915(19), N2ϪC20 1.5120(17), omitted for clarity; ellipsoids at 50% probability level; selected
˚
N2ϪC24 1.4978(18), N2ϪC25 1.4952(16), C13ϪC18 1.502(2), bond lengths [A] and angles [°]: C1ϪC2 1.199(2), C2ϪC3 1.429(2),
C18ϪC19 1.322(2), C23ϪC28 1.5070(19), C28ϪC29 1.311(2),
C3ϪC4 1.343(2), C4ϪC5 1.428(2), C5ϪC6 1.197(2), C1ϪC14
C(aliph.)Ϫ(aliph.) 1.515(2)Ϫ1.5559(19),
O1···Hw2 2.01(3); 1.467(2), C6ϪC24 1.467(2), N1ϪC11 1.4893(19), N1ϪC15
1.4732(18), N1ϪC17 1.4893(17), N2ϪC21 1.484(2), N2ϪC25
O1ϪPd1ϪN1 85.99(4), N1ϪPd1ϪO2 93.14(4), O2ϪPd1ϪN2
85.94(4), N2ϪPd1ϪO1 94.91(4), C10ϪN1ϪPd1 104.87(8), 1.468(2), N2ϪC27 1.4804(19), C(aliph.)ϪC(aliph.) 1.507(3) to
C14ϪN1ϪPd1 111.92(8), C15ϪN1ϪPd1 114.12(8), C20ϪN2ϪPd1 1.573(2); C2ϪC1ϪC14 177.94(15), C1ϪC2ϪC3 176.98(15),
104.49(8), C24ϪN2ϪPd1 111.81(8), C25ϪN2ϪPd1 114.15(8),
C2ϪC3ϪC4 125.56(13), C3ϪC4ϪC5 125.16(13), C4ϪC5ϪC6
C14ϪC13ϪC18
112.03(12),
C24ϪC23ϪC28
112.34(11), 177.23(15), C5ϪC6ϪC24 176.72(15), C17ϪC18ϪO1 113.80(13),
C27ϪC28ϪO2 113.97(16)
C13ϪC18ϪC19 125.93(19), C23ϪC28ϪC29 125.04(15)
Scheme 4. The synthesis of didehydro-QCI (13) and didehydro-QCD (14)
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PdII and PtII Complexes with Quincorine and Quincoridine Derivatives
FULL PAPER
Both compounds crystallised with water molecules (9: one; Ϫx ϩ 2, y ϩ 0.5, Ϫz ϩ 0.5] leads to the formation of zig-
11: two). In complex 9 intra- and intermolecular hydrogen- zag chains parallel to the crystallographic b-axis in the crys-
i
bonding [OϪH···O: H···O 207(2)i, 201(3) pm; x, y ϩ 1, tal packing (Figure 8).5
z] forms chains, which are also connected by non-classical
Treatment of 17 and 18 with chlorodiphenylphosphane
ii
CϪH···O hydrogen-bonding [H···O 266ii, 248 pmiii; Ϫ x in dichloromethane, in the presence of triethylamine, gave
iii
ϩ 2, y Ϫ 0.5, Ϫz ϩ 1, Ϫ x ϩ 1, y ϩ 0.5, Ϫz ϩ 1]. The the bis-aminophosphinites 19 and 20 in very good yields
hydrogen-bonding scheme in 11 is similar, but with stronger (Scheme 5).
classical OϪH···O bonds [H···O 179(5), 192(3), 203(3)i,
These are pale yellow oils, which are stable under nitro-
i
ii
201(5) pmii; Ϫx, y Ϫ 0.5, Ϫz ϩ 1.5, x, y ϩ 1, z] and gen atmosphere for a long time. In the 31P{1H} NMR spec-
comparable non-classical CϪH···O bonds [H···O: 263i, 233i, tra the resonances of the P atoms are found at δ ϭ 115.29
iii
iv
254iii, 251 pmiv; Ϫ x ϩ 1, y ϩ 0.5, Ϫz ϩ 1.5, Ϫx, y ϩ (19) and δ ϭ 114.60 ppm (20), respectively.
0.5, Ϫz ϩ 1.5]. Again, the bond lengths in the molecules
are unexceptional and match the usual observed ranges.
Platinum(II) and Palladium(II) Complexes
The bis-N,P-aminophosphinites 19 and 20, having two
soft electron-donating atoms and two hard electron-donat-
N,P-Ligand Synthesis
For the synthesis of N,P-ligands we used 10,11-dide- ing atoms, show different coordinating properties towards
hydroquincorine (13) and 10,11-didehydroquincoridine (14) PtII and PdII. It is known that the formation of square-
as precursors. The terminal alkynes 13 and 14 were pre- planar PtII complexes is strongly dependent on a number
pared efficiently from 1 and 2 according to a known litera- of factors, such as solvent polarity, the trans effect of the
ture procedure (Scheme 4).[13]
resident ligands, and the order of adding the reactants.
The symmetrical (Z)-enediynes 17 and 18 were obtained When phosphorus is coordinated to 195Pt, the geometry of
in good yields in a two-step procedure[14,15] involving two the products can often be assigned from the magnitude of
sequential [Pd(PPh3)4]- and [PdCl2(PhCN)2]-catalysed the coupling constants. These are strongly dependent on the
coupling reactions from (Z)-1,2-dichloroethene and 13 and
14. Colourless single crystals of 18 were obtained by layer-
ing a CH2Cl2 solution with hexanes. A structure determi-
nation revealed a cis-arrangement in the molecule (Fig-
ure 7).
Classical hydrogen-bonding of the type OϪH···N [H···N:
i
ii
196(3)i, 203(3) pmii; Ϫx ϩ 1, y Ϫ 0.5, Ϫz ϩ 0.5; Ϫ x ϩ
1, y ϩ 0.5, Ϫz ϩ 0.5] together with non-classical CϪH···O
iii
iv
hydrogen-bonding [H···O: 257iii, 245 pmiv; x ϩ 1, y, z;
Figure 9. The molecular structure of 21; hydrogen atoms and the
disordered THF molecule are omitted for clarity; ellipsoids at 50%
˚
probability level; selected bond lengths [A] and angles [°] (corre-
sponding values of the second independent molecule in the asym-
metric unit are given in brackets): Pt1ϪP1 2.2231(19) [2.2291(18)],
PtϪ1P2 2.229(2) [2.2349(18)], Pt1ϪCl1 2.3642(19) [2.3564(18)],
Pt1ϪCl2 2.3532(19) [2.3536(18)], P1ϪO1 1.587(5) [1.597(5)],
P2ϪO2 1.600(4) [1.601(4)], O1ϪC18 1.466(7) [1.459(6)], O2ϪC28
1.438(6) [1.442(6)], C1ϪC2 1.176(9) [1.204(9)], C2ϪC3 1.470(10)
[1.473(11)], C3ϪC4 1.328(10) [1.299(14)], C4ϪC5 1.429(9)
[1.363(15)], C5ϪC6 1.191(9) [1.227(15)], C1ϪC14 1.482(9)
[1.459(8)], C6ϪC24 1.481(8) [1.415(15)], N1ϪC11 1.483(7)
[1.456(6)], N1ϪC15 1.453(7) [1.461(7)], N1ϪC16 1.486(7)
[1.490(8)], N2ϪC21 1.488(6) [1.515(8)], N2ϪC25 1.457(7)
[1.478(10)], N2ϪC26 1.471(7) [1.501(12)], C(aliph.)ϪC(aliph.)
1.509(9)Ϫ1.580(7) [1.496(7)Ϫ1.583(11)]; P1ϪPt1ϪP2 94.17(7)
[93.23(7)], P1ϪPt1ϪCl1 85.41(7) [93.51(7)], P2ϪPt1ϪCl2 92.07(7)
[85.85(7)], Cl1ϪPt1ϪCl2 88.29(7) [87.29(7)], C18ϪO1ϪP1 122.1(4)
[116.2(3)], C28ϪO2ϪP2 127.5(4) [128.8(4)], O1ϪC18ϪC11
109.9(4)
[111.0(4)],
O2ϪC28ϪC21
107.9(4)
[107.8(4)],
Figure 8. The packing of 18 in the crystal showing the hydrogen
bonding; view along the a axis; molecules contain the OH group;
other hydrogens omitted
C14ϪC1ϪC2 174.9(7) [177.3(7)], C1ϪC2ϪC3 176.0(7) [175.9(9)],
C2ϪC3ϪC4 122.8(7) [126.3(10)], C3ϪC4ϪC5 128.6(7) [127.3(9)],
C4ϪC5ϪC6 176.4(7) [176.9(10)], C5ϪC6ϪC24 175.9(6) [176.6(10)]
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Scheme 5. The synthesis of the bis-N,P-aminophosphinites 19 and 20 from didehydro-QCI (13) and didehydro-QCD (14)
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PdII and PtII Complexes with Quincorine and Quincoridine Derivatives
FULL PAPER
Scheme 6. Platinum() chelate complexes of the bis-N,P-aminophosphinites 19 and 20
ligand trans to the phosphorus atom, because of the induc- somewhat wider than 90° [94.17(7), 93.23(7)°]. The ligand
tive effect of that ligand on the platinum-phosphorus bond. is bound symmetrically with similar PtϪP bond lengths
Ligands with a very strong σ-inductive character reduce the [222.31(19), 222.9(2); 222.91(18), 223.49(18) pm, respec-
positive charge on the platinum atom and thus weaken the tively].
overlap of the phosphorus and the metal orbitals relative to
Attempts to synthesise the corresponding trans complex
from 20 through the inverse addition of the reactants led,
the trans-ligands, which have weaker σ-inductive effects.[16]
When a solution of [PtCl2(SMe2)2] in dichloromethane after 30 minutes at room temperature, to a complex mixture
was added to a solution of 19 or 20 in the same solvent, in of products. The 31P{1H} NMR spectrum of this mixture
a 1:1 molar ratio, the cis complexes 21 and 22 were ob- displays many signals with different intensities and corre-
tained (Scheme 6).
sponding 195Pt satellites, including the signal of the reac-
In the 31P{1H} NMR spectra singlets, with 195Pt satel- tant. After 24 h at room temperature the cis complex 22
lites, at δ ϭ 83.89 ppm (1JPt,P ϭ 2099.28 Hz) (21) and δ ϭ became the main product observed by 31P NMR spec-
85.10 ppm (1JPt,P ϭ 2076.01 Hz) (22) are observed. The troscopy. Treatment of two equivalents of [PtCl2(SMe2)2]
FAB mass spectra indicated that the complexes are mono- with one equivalent of 20, in dichloromethane, again pro-
meric. Slow diffusion of diethyl ether into a concentrated duced the cis complex 22.
THF/dioxane solution of the complex 21 produced colour-
Armstrong and co-workers have reported recently that
less crystals that crystallised in the non-centrosymmetric the bis-phosphane ligands 2,7-bis(3-diphenylphosphanylp-
space group P1 with two independent molecules of 21 and ropoxy)naphthalene (DPPN) and 2,7-bis(3-diphenylphos-
one disordered and badly resolved THF molecule per for- phanylethoxy)naphthalene (DPEN) form dimeric cis, cis/
mula unit (Figure 9).
trans and trans complexes of platinum() depending on the
The complex can be regarded as a 21-membered ring sys- conditions employed.[17] They have also demonstrated that
tem with a PtCl2 group that connects the phosphorus() an excess of the ligand catalyzes trans/cis isomerisation,
ends of the ligand to form a macrocyclic complex with an either by adding an excess of the phosphane, or by having
essentially planar coordination geometry at platinum (mean the excess present during the addition of the platinum pre-
dev. Pt1: 1.2; Pt2: 4.2 pm). Because of the steric demand of cursor. Based on these and our results we conclude that the
the aminophosphinite ligand, the bite angle at platinum is cis complexes 21 and 22 are the thermodynamic products.
Eur. J. Inorg. Chem. 2004, 749Ϫ761
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755

M. Fild, C. Thöne, S. Tötös
FULL PAPER
The complex mixture formed by the inverse addition of the field shifts of more than 1.5 ppm in comparison with the
reactants should be a mixture of kinetic and thermo- free ligands because of the anisotropy of the phenyl groups.
dynamic products and thus the free unchanged ligand has Secondly, in the 1H,1H-COSY spectra of 23 and 24 the
catalysed a trans/cis isomerisation. The ligands 19 and 20 cross-peaks corresponding to the vicinal correlations of the
show a marked preference to form cis-PϪMϪP-monomeric 2-H atom with the 9-H atoms disappear due to the chang-
metallamacrocycles with PtII centres, even though a 1:2 mo- ing of the dihedral angles through the closure of the six-
lar ratio was employed.
membered rings.
In view of the interesting complexes 21 and 22 we tried
In contrast to platinum(), palladium() shows a marked
to obtain the corresponding complexes with PdII. The re- preference to form bis-N,P-chelate complexes with ligands
sults were completely different. The reaction of one equiva- 19 and 20.
lent of 20 with one equivalent of [(η4-C7H8)PdCl2] in di-
chloromethane produced a yellow solid. The 31P{1H} NMR
spectrum of the crude product shows many singlets up to
δ ϭ 103 ppm. Attempts to isolate a pure complex from the
mixture were unsuccessful.
Conclusion
We have shown that the N,O-chelate complexes and bis-
When one equivalent of 19 or 20 was allowed to react N,O-chelate complexes of PdII with QCI and QCD and
with two equivalents of [(η4-C7H8)PdCl2] in dichlorometh- their saturated derivatives are easy to prepare. The synth-
ane yellow solids were again obtained (Scheme 7).
eses of two new bis-N,P-aminophosphinite ligands, derived
The 31P{1H} NMR spectra of these products show only from QCI and QCD, have been developed. Both ligands
one signal around δ ϭ 103 ppm. The ESI mass spectra indi- have two soft and hard donor-atoms that can be exploited
cated that the compounds are the bis-N,P-chelate com- to form mononuclear and binuclear chelate complexes.
plexes 23 and 24 (Scheme 5). The formation of the six-mem- Platinum() forms PϪMϪP metallamacrocycle complexes,
1
bered chelate rings in 23 and 24 is also confirmed by H but palladium() prefers to form bis-N,P-chelate complexes
NMR spectra. The 6b-H and 7a-H atoms undergo down- with these ligands.
Scheme 7. Dinuclear palladium() complexes of the bis-N,P-aminophosphinites 19 and 20
756
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PdII and PtII Complexes with Quincorine and Quincoridine Derivatives
FULL PAPER
H-4), 2.38Ϫ2.45 (m, 1 H, H-5), 3.08 (dd, J ϭ 11.98, J ϭ 4.79 Hz,
1 H, H-9), 3.13Ϫ3.21 (m, 1 H, H-2), 3.24Ϫ3.31 (m, 2 H, H-7, H-
6), 3.49Ϫ3.57 (m, 1 H, H-7), 3.65 (dd, J ϭ 13.12, J ϭ 10.23 Hz, 1
H, H-6), 3.73Ϫ3.79 (m, 1 H, 9), 5.00Ϫ5.04 (m, 2 H, 11), 5.70Ϫ5.79
(m, 1 H, 10), 7.26Ϫ7.38 (m, 9 H, Ph), 7.55Ϫ7.60 (m, 6 H, Ph) ppm.
13C NMR (100 MHz, CDCl3): δ ϭ 21.56 (C-3), 26.03 (C-8), 27.39
(C-4), 39.45 (C-5), 48.94 (C-6), 52.57 (C-7), 67.50 (C-2), 73.01 (C-
9), 115.64 (C-11), 128.03 (d, J ϭ 10.85 Hz, Ph o-C), 129.45 (d, J ϭ
51.47 Hz, Ph i-C), 130.56 (d, J ϭ 2.64 Hz, Ph p-C), 134.65 (d, J ϭ
1 1.00 Hz, Ph m-C), 138.43 (C-10) ppm. 31P NMR (162 MHz,
CDCl3): δ ϭ 26.83 (trans to N), 23.96 (cis to N) ppm. FAB: m/z ϭ
570 [M ϩ H]ϩ, 534 [M Ϫ Cl]ϩ.
Experimental Section
General Remarks: All reactions were performed under a dry nitro-
gen atmosphere using standard Schlenk techniques. CH2Cl2 was
freshly distilled under nitrogen from P4O10, THF was dried over
sodium/benzophenone and distilled prior to use. Et3N was heated
to reflux over sodium and distilled under nitrogen. Piperidine and
nBuNH2 were dried over NaOH and then distilled under nitrogen.
Ph2PCl and (Z)-1,2-dichloroethene were purchased from Aldrich.
Pd(PPh3)4,[18]
[PdCl2(PPh3)]2
[PdCl2(PhCN)2],[19]
[(η4-C7H8)PdCl2],[20]
[21]
and [PtCl2(SMe2)2][16] were prepared according
to literature procedures. QCI (1) and QCD (2) were donated by
Buchler GmbH. Dihydro-QCI (3), dihydro-QCD (4), didehydro-
QCI (13), and didehydro-QCD (14) were prepared according to
a literature procedure.[13] Preparative column chromatography was
performed on Fluka silica gel (particle size 30Ϫ60 µm). Analytical
TLC was carried out on Polygram Sil G/UV254 plates (0.2 mm silica
gel). tert-Butyl methyl ether (MTBE) was purchased from Fluka.
7: From
3 (100 mg, 0.6 mmol), NaOMe (0.6 mmol) and
[PdCl2(PPh3)]2 (263 mg, 0.3 mmol). C28H33ClNOPPd (572.42).
M.p. 175Ϫ176 °C. 1H NMR (400 MHz, CDCl3): δ ϭ 0.81Ϫ0.85 (t,
J ϭ 7.30 H, 3 H, CH2CH3), 0.95Ϫ1.00 (m, 1 H, H-3), 1.34Ϫ1.41
(m, 2 H, CH2CH3), 1.53Ϫ1.63 (m, 3 H, H-5, H-8), 1.72Ϫ1.81 (m,
2 H, H-3, H-4), 2.77Ϫ2.81 (m, 1 H, H-6), 3.07 (dd, J ϭ 11.68, J ϭ
4.32 Hz, 1 H, H-9), 3.13Ϫ3.24 (m, 1 H, H-2), 3.33Ϫ3.43 (m, 1 H,
H-7), 3.61Ϫ3.68 (m, 1 H, H-7), 3.74 (t, J ϭ 11.68 Hz, 1 H, H-9),
3.78 (dd, J ϭ 13.38, J ϭ 10.35 Hz, 1 H, H-6), 7.26Ϫ7.38 (m, 9 H,
Ph), 7.56Ϫ7.62 (m, 6 H, Ph) ppm. 13C NMR (100 MHz, CDCl3):
δ ϭ 12.00 (CH2CH3), 21.98 (C-3), 24.84 (C-4), 27.92 (CH2CH3),
28.35 (C-8), 37.84 (C-5), 43.56 (C-7), 59.97 (C-6), 68.02 (C-2), 73.69
(C-9), 128.05 (d, J ϭ 10.84 Hz, Ph o-C), 129.14 (d, J ϭ 51.31 Hz,
Ph i-C), 130.56 (d, J ϭ 2.60 Hz, Ph p-C), 134.71 (d, J ϭ 11.00 Hz,
Ph m-C), ppm. 31P NMR (162 MHz, CDCl3): δ ϭ 26.82 (trans to
N), 26.74 (cis to N) ppm. FAB: m/z ϭ 572 [M ϩ H]ϩ, 536 [M
Ϫ Cl]ϩ.
NMR spectra were obtained from CD2Cl2, CDCl3 and C6D6 solu-
tions. 1H, 13C and 31P NMR spectra were recorded using a Bruker
DRX-400 spectrometer operating at 400, 100 and 162 MHz,
respectively. Chemical shifts (δ) are given in ppm relative to residual
CHCl3 (δ ϭ 7.27 ppm), CH2Cl2 (δ ϭ 5.31 ppm) or C6H6 (δ ϭ
1
7.16 ppm) for H, CDCl3 (δ ϭ 77.0 ppm), CD2Cl2 (δ ϭ 53.7 ppm)
or C6D6 (δ ϭ 128.7 ppm) for 13C, and 85% H3PO4 (δ ϭ 0.0 ppm,
external) for 31P. Coupling constants (J) are given in Hz. Mass
spectra were obtained using a Finnigan MAT 90 spectrometer op-
erating in FAB and ESI mode for coordination complexes (the iso-
tope patterns matched calculated patterns in all cases), and in EI
mode for the organic precursors. In all cases precision mass analy-
ses confirmed the purity of the products. Melting points were deter-
mined on a Büchi 510 Melting Point apparatus and are uncor-
rected.
8: From
4 (100 mg, 0.6 mmol), NaOMe (0.6 mmol) and
[PdCl2(PPh3)]2 (263 mg, 0.3 mmol). C28H33ClNOPPd (572.42).
M.p. 130Ϫ132 °C. 1H NMR (400 MHz, CDCl3): δ ϭ 0.80Ϫ0.84 (t,
J ϭ 7.39 Hz, 3 H, CH2CH3), 1.20Ϫ1.36 (m, 3 H, 3, CH2CH3),
1.45Ϫ1.52 (m, 1 H, H-3), 1.56Ϫ1.73 (m, 4 H, H-8, H-5, H-4),
2.99Ϫ3.26 (m, 4 H, H-7, H-2, H-9, H-6), 3.46Ϫ3.54 (m, 1 H, H-
7), 3.58Ϫ3.64 (m, 1 H, H-6), 3.76 (t, J ϭ 11.35 Hz, 1 H, H-9),
7.26Ϫ7.37 (m, 9 H, Ph), 7.56Ϫ7.61 (m, 6 H, Ph) ppm. 13C NMR
(100 MHz, CDCl3): δ ϭ 11.74 (CH2CH3), 21.35 (C-3), 25.13
(CH2CH3), 25.80 (C-4), 26.74 (C-8), 37.36 (C-5), 51.05 (C-6), 52.74
(C-7), 67.85 (C-2), 73.22 (C-9), 128.00 (d, J ϭ 10.86 Hz, Ph o-C),
129.57 (d, J ϭ 51.18 Hz, Ph i-C), 130.50 (d, J ϭ 2.62 Hz, Ph p-C),
134.66 (d, J ϭ 10.99 Hz, Ph m-C) ppm. 31P NMR (162 MHz,
CDCl3): δ ϭ 26.78 (cis to N) 26.64 (trans to N) ppm. FAB: m/z ϭ
572 [M ϩ H]ϩ, 536 [M Ϫ Cl]ϩ.
General Procedure for the Preparation of the PdII-Phosphane Com-
plexes 5؊8: A solution of ligand 1Ϫ4 and NaOMe in CH2Cl2/
MeOH (1:1) was added dropwise to a suspension of [PdCl2(PPh3)]2
in CH2Cl2 and the mixture was stirred for 3 h at room temperature.
The solvent was then removed under vacuum and the residue was
dissolved again in CH2Cl2 and stirred for 15 minutes. The suspen-
sion was filtered to removed NaCl and the resulting clear solution
was concentrated to dryness. The crude product was recrystallised
from diethyl ether and n-hexane.
5: From
1 (100 mg, 0.6 mmol), NaOMe (0.6 mmol) and
[PdCl2(PPh3)]2 (263 mg, 0.3 mmol). C28H31ClNOPPd (570.41).
General Procedure for the Preparation of the Homoleptic PdII Com-
M.p. 158Ϫ165 °C. 1H NMR (400 MHz, CDCl3): δ ϭ 0.96Ϫ1.02 plexes 9؊12: A solution of ligand 1؊4 and NaOMe in CH2Cl2/
(m, 1 H, H-3), 1.55Ϫ1.67 (m, 2 H, H-8), 1.76Ϫ1.79 (m, 1 H, H-4), MeOH (1:1) was added dropwise to a solution of [PdCl2(PhCN)2]
1.80Ϫ1.87 (m, 1 H, H-3), 2.32Ϫ2.43 (m, 1 H, H-5), 3.06Ϫ3.12 (m,
2 H, H-6, H-9), 3.16Ϫ3.24 (m, 1 H, H-2), 3.36Ϫ3.43 (m, 1 H, H-
in CH2Cl2 and the reaction mixture was stirred for 1 h at room
temperature. The solvent was removed from the light yellow sus-
7), 3.61Ϫ3.69 (m, 1 H, H-7), 3.74 (t, J ϭ 11.44 Hz, 1 H, H-9), 3.81 pension under vacuum and the residue was dissolved again in
(dd, J ϭ 13.7, J ϭ 10.62 Hz, 1 H, H-6), 5.00Ϫ5.07 (m, 2 H, 11), CH2Cl2 and stirred for 15 minutes. The suspension was filtered to
5.77Ϫ5.86 (m, 1 H, 10), 7.26Ϫ7.38 (m, 9 H, Ph), 7.56Ϫ7.61 (m, 6 remove NaCl and the resulting yellow solution was concentrated
H, Ph) ppm. 13C NMR (100 MHz, CDCl3): δ ϭ 22.26 (C-3), 27.13 to dryness. The crude product was recrystallised from diethyl ether
(C-4), 27.72 (C-8), 39.62 (C-5), 43.50 (C-7), 58.09 (C-6), 67.96 (C-
2), 73.57 (C-9), 115.22 (C-11), 128.03 (d, J ϭ 10.85 Hz, Ph o-C), 9: From
129.51 (d, J ϭ 51.52 Hz, Ph i-C), 130.56 (d, J ϭ 2.63 Hz, Ph p-C), [PdCl2(PhCN)2] (460 mg, 1.2 mmol). C20H32N2O2Pd (438.91). M.p.
and n-hexane.
1
(400 mg, 2.4 mmol), 2.4 mmol of NaOMe and
1
134.67 (d, J ϭ 10.98 Hz, Ph m-C), 140.57 (C-10) ppm. 31P NMR
(162 MHz, CDCl3): δ ϭ 26.84 (trans to N), 23.95 (cis to N) ppm. H, H-3), 1.55Ϫ1.63 (m, 4 H, H-8), 1.73Ϫ1.83 (m, 4 H, H-H-3, H-
FAB: m/z ϭ 570 [M ϩ H]ϩ, 534 [M Ϫ Cl]ϩ.
4), 2.38Ϫ2.42 (m, 2 H, H-5), 2.92 (dd, J ϭ 11.21, J ϭ 5.17 Hz, 2
6: From (100 mg, 0.6 mmol), NaOMe (0.6 mmol) and H, H-9), 3.00Ϫ3.18 (m, 8 H, H-6, H-7, H-2), 3.44Ϫ3.49 (m, 2 H,
[PdCl2(PPh3)]2 (263 mg, 0.3 mmol). C28H31ClNOPPd (570.41). H-9), 3.69Ϫ3.78 (m, 2 H, H-7), 5.07Ϫ5.13 (m, 4 H, H-11),
M.p. 152Ϫ155 °C. 1H NMR (400 MHz, CDCl3): δ ϭ 1.25Ϫ1.31 5.93Ϫ5.84 (m, 2 H, H-10) ppm. 13C NMR (100 MHz, CD2Cl2):
(m, 1 H, H-3), 1.49Ϫ1.56 (m, 1 H, H-3), 1.62Ϫ1.72 (m, 3 H, H-8, δ ϭ 22.35 (C-3), 27.11 (C-4), 27.79 (C-8), 39.63 (C-5), 45.60 (C-7),
152Ϫ155 °C. H NMR (400 MHz, CD2Cl2): δ ϭ 0.93Ϫ0.98 (m, 2
2
Eur. J. Inorg. Chem. 2004, 749Ϫ761
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757

M. Fild, C. Thöne, S. Tötös
FULL PAPER
58.89 (C-6), 69.38 (C-2), 70.95 (C-9), 115.14 (C-11), 140.96 (C-10). ppm. MS-EI (43 °C): m/z (%) ϭ 227 (18) [Mϩ], 225 (48) [Mϩ], 194
EI: m/z ϭ 438 [M]ϩ, 408 [M Ϫ CH2O]ϩ, 378 [M Ϫ 2CH2O]ϩ.
(270 mg, 1.6 mmol), 1.6 mmol of NaOMe and
(78), 190 (100), 162 (12), 159 (30), 132 (78), 126 (31), 103 (24), 82
10: From
3
(16), 77 (26), 72 (29), 63 (14), 55 (21), 51 (10), 44 (44). EI: m/z ϭ
[PdCl2(PhCN)2] (300 mg, 0.8 mmol). C20H36N2O2Pd (442.94). M.p. 225 [M]ϩ, 194 [M Ϫ CH2OH]ϩ, 190 [M Ϫ Cl]ϩ.
144Ϫ147 °C. 1H NMR (400 MHz, CD2Cl2): δ ϭ 0.85Ϫ0.89 (t, J ϭ
16: From 13 (2 g, 12 mmol), [Pd(PPh3)4] (0.69 g, 0.59 mmol), CuI
7.34 Hz, 6 H, CH2CH3), 0.90Ϫ0.95 (m, 2 H, H-3), 1.37Ϫ1.45 (m,
4 H, CH2CH3), 1.48Ϫ1.78 (m, 10 H, H-3, H-4, H-8, H-5),
2.68Ϫ2.73 (m, 2 H, H-6), 2.91 (dd, J ϭ 11.1, J ϭ 5.16 Hz, 2 H, H-
9), 3.04Ϫ3.14 (m, 6 H, H-6, H-7, H-2), 3.44 (t, J ϭ 11.1 Hz, 2 H,
H-9), 3.76Ϫ3.68 (m, 2 H, H-7) ppm. 13C NMR (100 MHz,
CD2Cl2): δ ϭ 11.98 (CH2CH3), 22.04 (C-3), 24.63 (C-4), 28.04
(CH2CH3), 28.38 (C-8), 37.76 (C-5), 45.65 (C-7), 60.88 (C-6), 69.34
(2), 70.99 (C-9). EI: m/z ϭ 442 [M]ϩ, 412 [M Ϫ CH2O]ϩ, 382 [M
Ϫ 2CH2O]ϩ.
(0.23 g, 1.2 mmol), nBuNH2 (2.06 g, 23.95 mmol) and (Z)-1,2-
dichloroethene (3.49 g, 36 mmol). C12H16ClNO (225.5). H NMR
1
(400 MHz, CDCl3): δ ϭ 1.38Ϫ1.62 (m, 4 H, H-8, H-3), 1.87Ϫ1.91
(m, 1 H, H-4), 2.59Ϫ2.63 (m, 1 H, H-5), 2.74Ϫ3.00 (m, 5 H, H-6,
H-2, H-7), 3.31 (s, 1 H, OH), 3.57 (t, J ϭ 11.24 Hz, 1 H, H-9), 5.78
(dd, J ϭ 7.34, J ϭ 2.23 Hz, 1 H, H-12), 6.26 (d, J ϭ 7.34 Hz, 1 H,
H-13) ppm. 13C NMR (100 MHz, CDCl3): δ ϭ 24.19 (C-13), 25.45
(C-8), 27.28 (C-4), 29.33 (C-5), 47.83 (C-6), 48.42 (C-7), 57.23 (C-
2), 62.03 (C-9), 75.60 (C-11), 101.37 (C-10), 112.14 (C-12), 127.46
(C-13) ppm. MS-EI (55 °C): m/z (%) ϭ 227 (24) [Mϩ], 225 (79)
[Mϩ], 208 (4), 194 (100), 190 (88), 158 (22), 132 (48), 126 (64), 117
(16), 112 (25), 103 (34), 82 (32), 77 (31), 72 (49), 63 (14), 55 (35),
51 (16), 44 (48), 42 (68). EI: m/z ϭ 225 [M]ϩ, 194 [M Ϫ CH2OH]ϩ,
190 [M Ϫ Cl]ϩ.
11: From
2 (400 mg, 2.4 mmol), 2.4 mmol of NaOMe and
[PdCl2(PhCN)2] (460 mg, 1.2 mmol). C20H32N2O2Pd (438.91). M.p.
1
155Ϫ160 °C. H NMR (400 MHz, CD2Cl2): δ ϭ 1.21Ϫ1.26 (m, 2
H, H-3), 1.45Ϫ1.52 (m, 2 H, H-3), 1.58Ϫ1.76 (m, 6 H, H-8, H-2),
2.36Ϫ2.42 (m, 2 H, H-5), 2.88Ϫ2.95 (m, 4 H, H-9, H-7), 2.98Ϫ3.07
(m, 2 H, H-9), 3.16Ϫ3.23 (m, 2 H, H-7), 3.33 (dd, J ϭ 13.34, J ϭ
10.21 Hz, 2 H, H-6), 3.38Ϫ3.44 (ddd, J ϭ 13.34, J ϭ 8.42, J ϭ
2.18 Hz, 2 H, H-6), 3.50 (t, J ϭ 10.96 Hz, 2 H, H-9), 5.05Ϫ5.10 (m,
4 H, H-11), 5.84Ϫ5.75 (m, 2 H, H-10) ppm. 13C NMR (100 MHz,
CD2Cl2): δ ϭ 21.66 (C-3), 25.95 (C8), 27.84 (C-4), 39.78 (C-5),
50.93 (C-6), 53.34 (C-7), 69.20 (C-2), 70.88 (C-9), 115.45 (C-11),
138.97 (C-10). EI: m/z ϭ 438 [M]ϩ, 408 [M Ϫ CH2O]ϩ, 378 [M
Ϫ 2CH2O]ϩ.
General Procedure for the Preparation of the Enediynes 17 and 18:
[PdCl2(PhCN)2] (0.05 equiv.), piperidine (2 equiv.) and terminal al-
kyne (1.2 equiv.) were added to a solution of pure chloroenyne (1
equiv.) in absolute THF, at room temperature, under a nitrogen
atmosphere. CuI (0.1 equiv.) was then added to the stirred solution.
The stirring was continued until TLC analysis indicated complete
consumption of the chloroenyne. The reaction mixture was treated
with a saturated aqueous solution of NaHCO3 and extracted with
CH2Cl2. The organic layer was dried over Na2SO4 and the solvent
was removed in vacuo. The resulting crude product was purified by
column chromatography [MTBE/MeOH/NH3(25%)] to afford the
desired enediyne.
17: From 15 (2.32 g, 10.28 mmol), [PdCl2(PhCN)2] (197 mg,
0.5 mmol), CuI (196 mg, 1.02 mmol), piperidine (1.76 g,
20.46 mmol) and 13 (1.86 g, 11.27 mmol). C22H30N2O2 (354). 1H
NMR (400 MHz, CDCl3): δ ϭ 0.74Ϫ0.80 (m, 2 H, H-3), 1.34Ϫ1.49
(m, 4 H, H-8), 1.86Ϫ1.90 (m, 2 H, H-4), 2.03Ϫ2.10 (m, 2 H, H-3),
2.49Ϫ2.56 (m, 2 H, H-7), 2.66Ϫ2.68 (m, 2 H, H-5), 2.82Ϫ2.92 (m,
4 H, H-7, H-6), 3.02Ϫ3.10 (m, 2 H, H-2), 3.23 (dd, J ϭ 13.15, J ϭ
9.94 Hz, 2 H, H-6), 3.31Ϫ3.46 (m, 6 H, H-9, OH), 5.70 (s, 2 H, H-
12) ppm. 13C NMR (100 MHz, CDCl3): δ ϭ 25.08 (C-3), 26.18 (C-
8), 26.65 (C-4), 29.03 (C-5), 39.64 (C-7), 56.95 (C-2), 57.12 (C-6),
62.76 (C-9), 78.69 (C-11), 100.91 (C-10), 118.96 (C-12) ppm. MS-
EI (163 °C): m/z (%) ϭ 354 (100) [Mϩ], 337 (2), 323 (45), 297 (25),
295 (12), 277 (8), 265 (16), 242 (10), 238 (12), 224 (7), 210(17), 184
(14), 177 (7), 165 (11), 141 (8), 128 (13), 115 (12), 100 (9), 96 (10),
86 (12), 70 (14), 55 814), 44 (27), 42 (24). EI: m/z ϭ 354 [M]ϩ, 323
[M Ϫ CH2OH]ϩ.
12: From
4 (100 mg, 0.6 mmol), 0.6 mmol of NaOMe and
[PdCl2(PhCN)2] (113 mg, 0.3 mmol). C20H36N2O2Pd (442.94). M.p.
180Ϫ182 °C. 1H NMR (400 MHz, CD2Cl2): δ ϭ 0.77Ϫ0.81 (t, J ϭ
7.39 Hz, CH2CH3), 1.10Ϫ1.32 (m, 6 H, 3, CH2CH3), 1.36Ϫ1.42
(m, 2 H, H-3), 1.45Ϫ1.55 (m, 6 H, H-5, H-4, H-8), 1.61Ϫ1.68 (m,
2 H, H-8), 2.84Ϫ2.91 (m, 2 H, H-7), 2.95Ϫ3.10 (m, 6 H, H-6, H-
2, H-9), 3.16Ϫ3.22 (m, 2 H, H-7), 3.3 (dd, J ϭ 13.13, J ϭ 9.84 Hz, 2
H, H-6), 3.5 (t, J ϭ 12.43 Hz, 2 H, H-9) ppm. 13C NMR (100 MHz,
CD2Cl2): δ ϭ 11.62 (CH2CH3), 21.21 (C-3), 25.12 (CH2CH3), 25.39
(C-4), 26.33 (C-8), 37.36 (C-5), 52.92 (C-6), 53.25 (C-7), 68.72 (C-
2), 70.59 (C-9). EI: m/z ϭ 442 [M]ϩ, 412 [M Ϫ CH2O]ϩ, 382 [M
Ϫ 2CH2O]ϩ.
General Procedure for the Preparation of the Chloroenynes 15 and
16: A mixture of [Pd(PPh3)4] (0.05 equiv.), (Z)-1,2-dichloroethene
(3 equiv.), alkyne (1 equiv.), and piperidine or nBuNH2 (2 equiv.)
in absolute THF was stirred for 15 minutes at room temperature
under a nitrogen atmosphere, and CuI (0.1 equiv.) was then added.
The stirring was continued until TLC analysis indicated complete
consumption of the alkyne (3Ϫ5 h). The reaction mixture was
treated with a saturated aqueous solution of NaHCO3 and ex-
tracted with CH2Cl2. The organic layer was dried over Na2SO4 and
the solvent was removed in vacuo. The crude product was purified
by column chromatography [MTBE/MeOH/NH3(25%)] to yield the
desired chloroenyne.
18: From 16 (1.05 g, 4.65 mmol), [PdCl2(PhCN)2] (90 mg,
0.2 mmol), CuI (88 mg, 0.46 mmol), piperidine (0.8 g, 9.3 mmol)
and 14 (0.92 g, 5.57 mmol). C22H30N2O2 (354). 1H NMR
(400 MHz, CDCl3): δ ϭ 1.36Ϫ1.62 (m, 8 H, H-8, H-3), 1.87Ϫ1.88
(m, 2 H, H-4), 2.62Ϫ2.66 (m, 2 H, H-5), 2.74Ϫ3.00 (m, 10 H, H-
15: From 13 (2 g, 12 mmol), [Pd(PPh3)4] (0.69 g, 0.59 mmol), CuI
(0.23 g, 1.2 mmol), nBuNH2 (1.75 g, 23.9 mmol) and (Z)-1,2-
1
dichloroethene (3.49 g, 36 mmol). C12H16ClNO (225.5). H NMR
(400 MHz, CDCl3): δ ϭ 0.74Ϫ0.80 (m, 1 H, H-3), 1.34Ϫ1.49 (m, 6, H-2, H-7), 3.07 (s, 2 H, OH), 3.39 (dd, J ϭ 11.1, J ϭ 5 Hz, 2 H,
2 H, H-8), 1.89Ϫ1.93 (m, 1 H, H-4), 2.04Ϫ2.11 (m, 1 H, H-3), H-9), 3.55 (t, J ϭ 11.1 Hz, 2 H, H-9), 5.69 (s, 2 H, H-12) ppm. 13
C
2.49Ϫ2.57 (m, 1 H, H-7), 2.65Ϫ2.68 (m, 1 H, H-5), 2.85Ϫ2.93 (m, NMR (100 MHz, CDCl3): δ ϭ 24.35 (C-3), 25.55 (C-8), 27.43 (C-
2 H, H-7, H-6), 3.06Ϫ3.11 (m, 2 H, H-2, OH), 3.23 (dd, J ϭ 13.17, 4), 29.45 (C-5), 48.01 (C-6), 48.43 (C-7), 57.13 (C-2), 62.14 (C-9),
J ϭ 9.95 Hz, 1 H, H-6), 3.38Ϫ3.45 (m, 2 H, H-9), 5.79 (dd, J ϭ
7.33, J ϭ 2.23 Hz, 1 H, H-12), 6.26 (d, J ϭ 7.33 Hz, 1 H, H-13) m/z (%) ϭ 354 (100) [Mϩ], 323 (21), 297 (9), 295 (13), 279 (16), 268
ppm. 13C NMR (100 MHz, CDCl3): δ ϭ 24.91 (C-3), 26.18 (C-8),
(5), 252 (3), 242 (8), 222 (6), 210 (9), 196 (9), 182 (11), 167 (29),
79.24 (C-11), 100.17 (C-10), 118.99 (C-12), ppm. MS-EI (132 °C):
26.56 (C-4), 28.95 (C-5), 39.55 (C-7), 56.82 (C-2), 56.88 (C-6), 62.61 149 (47), 126 (11), 115 (10), 108 (7), 96 (11), 86 (8), 71 (13), 57 (17),
(C-9), 75.09 (C-11), 102.02 (C-10), 112.20 (C-12), 127.39 (C-13) 44 (19), 42 (12). EI: m/z ϭ 354 [M]ϩ, 323 [M Ϫ CH2OH]ϩ.
758
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 749Ϫ761

PdII and PtII Complexes with Quincorine and Quincoridine Derivatives
FULL PAPER
General Procedure for the Preparation of the Bis-N,P-aminophosphin- 4), 28.57 (C-5), 40.44 (C-7), 54.89 (d, J ϭ 8.02 Hz, C-2), 56.86 (C-
ites 19 and 20: A solution of Ph2PCl (2.05 equiv.) in dry CH2Cl2 6), 68.42 (C-9), 78.42 (C-11), 100.81 (C-10), 118.77 (C-12), 127.85
was cooled to 0 °C and then a solution of (Z)-enediyne (1 equiv.) (d, J ϭ 11.73 Hz, Ph m-C), 128.25 (d, J ϭ 12.05 Hz, Ph m-C),
and NEt3 (4 equiv.) in the same solvent was added dropwise. After 131.40 (d, J ϭ 69.43, Ph i-C), 131.56 (Ph p-C), 131.75 (Ph p-C),
the addition, the reaction mixture was allowed to warm up to room
132.41 (d, J ϭ 12.34 Hz, Ph o-C), 132.45 (d, J ϭ 77.80 Hz, Ph i-
temperature and stirred until TLC analysis indicated complete con- C), 132.70 (d, J ϭ 11.58 Hz, Ph o-C) ppm. 31P NMR (162 MHz,
sumption of the reactant 17 and 18. The solution was concentrated
in vacuo and the residue was dissolved in CH2Cl2/n-hexane (1:2)
and stirred for 15 minutes. The suspension was filtered to remove
Et3N·HCl and the resulting clear solution was concentrated to dry-
ness. The crude product was purified by column chromatography
CDCl3): δ ϭ 83.89 (1JPt,P ϭ 2099.28 Hz) ppm. FAB: m/z ϭ 988
[M]ϩ, 953 [M Ϫ Cl]ϩ.
22: From 20 (250 mg, 0.346 mmol) and [PtCl2(SMe2)2] (135 mg,
0.346 mmol). M.p. 215 °C. C46H48Cl2N2O2P2Pt (988.83). 1H NMR
(400 MHz, CDCl3): δ ϭ 1.46Ϫ1.56 (m, 8 H, H-8, H-3), 1.92 (br. s,
under a nitrogen atmosphere (MTBE/acetonitrile/NEt3) to afford 2 H, H-4), 2.28Ϫ2.32 (m, 2 H, H-2), 2.62Ϫ2.75 (m, 8 H, H-7, H-
the desired bis-aminophosphinite in very good yield.
5, H-6), 2.94Ϫ3.01 (m, 2 H, H-6), 3.73Ϫ3.82 (m, 2 H, H-9),
4.07Ϫ4.09 (m, 2 H, H-9), 5.79 (s, 2 H, H-12), 7.25Ϫ7.36 (m, 12 H,
Ph), 7.66Ϫ7.71 (m, 4 H, Ph), 7.81Ϫ7.86 (m, 4 H, Ph) ppm. 13C
NMR (100 MHz, CDCl3): δ ϭ 24.70 (C-8), 25.34 (C-3), 27.13 (C-
4), 29.09 (C-5), 48.39 (C-7), 49.06 (C-6), 54.53 (d, J ϭ 6.93 Hz, C-
2), 70.27 (C-9), 79.12 (C-11), 100.10 (C-10), 119.03 (C-12), 127.84
(d, J ϭ 12.06 Hz, Ph m-C), 128.10 (d, J ϭ 11.89 Hz, Ph m-C),
131.40 (d, J ϭ 7.15 Hz, Ph p-C), 131.90 (d, J ϭ 11.86 Hz, Ph o-C),
132.47 (d, J ϭ 11.56 Hz, Ph o-C), 132.56 (d, J ϭ 74.00 Hz, Ph i-
C), 133.47 (d, J ϭ 75.00 Hz, Ph i-C) ppm. 31P NMR (162 MHz,
CDCl3): δ ϭ 85.10 (1JPt,P ϭ 2076.01 Hz) ppm. FAB: m/z ϭ 988
[M]ϩ, 953 [M Ϫ Cl]ϩ.
19: From 17 (1.22 g, 3.44 mmol), Ph2PCl (1.52 g, 6.8 mmol) and
NEt3 (13.7 mmol). C46H48N2O2P2 (722.85). 1H NMR (400 MHz,
C6D6): δ ϭ 0.75Ϫ0.80 (m, 2 H, H-3), 0.88Ϫ0.96 (m, 2 H, H-8),
1.00Ϫ1.08 (m, 2 H, H-8), 1.74Ϫ1.75 (m, 2 H, H-4), 2.13Ϫ2.18 (m,
2 H, H-3), 2.24Ϫ2.31 (m, 2 H, H-7), 2.43Ϫ2.45 (m, 2 H, H-5),
2.74Ϫ2.82 (m, 2 H, H-7), 2.92Ϫ3.04 (m, 4 H, H-6), 3.29Ϫ3.36 (m,
2 H, H-2), 3.64Ϫ3.70 (m, 2 H, H-9), 3.77Ϫ3.84 (m, 2 H, H-9), 5.59
(s, 2 H, H-12), 7.01Ϫ7.05 (m, 4 H, Ph), 7.09Ϫ7.13 (m, 8 H, Ph),
7.61Ϫ7.64 (m, 8 H, Ph) ppm. 13C NMR (100 MHz, C6D6): δ ϭ
25.75 (C-3), 26.46 (C-8), 27.65 (C-4), 29.32 (C-5), 41.04 (C-7), 56.68
(d, J ϭ 7.23 Hz, C-2), 71.71 (d, J ϭ 18.3 Hz, C-9), 57.81 (C-6),
79.41 (C-11), 101.79 (C-10), 119.47 (C-12), 128.43 (d, J ϭ 6.97 Hz,
Ph m-C), 128.50 (d, J ϭ 6.97 Hz, Ph m-C), 129.21 (d, J ϭ 3.35 Hz,
Ph p-C), 130.62 (d, J ϭ 8.32 Hz, Ph o-C), 130.83 (d, J ϭ 8.14 Hz,
Ph o-C), 143.31 (d, J ϭ 8.40 Hz, Ph i-C), 143.49 (d, J ϭ 7.83 Hz,
Ph i-C) ppm. 31P NMR (162 MHz, C6D6): δ ϭ 115.29 ppm. EI:
m/z ϭ 722 [M]ϩ, 521 [M Ϫ Ph2PO]ϩ, 201 [Ph2PO]ϩ.
General Procedure for the Preparation of the Binuclear PdII-N,P-
aminophosphinite Complexes 23 and 24: [(η4-C7H8)PdCl2] was ad-
ded to a solution of 19 or 20 in CH2Cl2 (20 mL) and the reaction
mixture was stirred overnight at room temperature. The solvent
of the clear yellow solution was removed under vacuum and the
remaining yellow solid was washed twice with n-hexane and dried
in vacuo for two days.
20: From 18 (1.36 g, 3.84 mmol), Ph2PCl (1.78 g, 8.00 mmol) and
1
NEt3 (15.36 mmol). C46H48N2O2P2 (722.85). H NMR (400 MHz,
23: From 19 (160 mg, 0.22 mmol) and [(η4-C7H8)PdCl2] (120 mg,
0.44 mmol). M.p. 210Ϫ214 °C. 1H NMR (400 MHz, CD2Cl2): δ ϭ
1.06Ϫ1.12 (m, 2 H, H-3), 1.49Ϫ1.67 (m, 4 H, H-8), 2.03 (br. s, 2
H, H-4), 2.25Ϫ2.31 (m, 2 H, H-3), 2.94Ϫ3.01 (m, 4 H, H-7, H-5),
3.19Ϫ3.24 (m, 4 H, H-6, H-2), 3.62Ϫ3.69 (m, 2 H, H-9), 3.84Ϫ3.95
(m, 2 H, H-9), 4.25Ϫ4.31 (m, 2 H, H-7), 5.09 (dd, J ϭ 13.56, J ϭ
10.4 Hz, 2 H, H-6), 5.80 (s, 2 H, H-12), 7.31Ϫ7.35 (m, 4 H, Ph),
7.42Ϫ7.47 (m, 6 H, Ph), 7.53Ϫ7.56 (m, 2 H, Ph), 7.59Ϫ7.65 (m, 4
H, Ph), 7.95Ϫ8.00 (m, 4 H, Ph) ppm. 13C NMR (100 MHz,
CD2Cl2): δ ϭ 26.09 (C-4), 26.64 (C-8), 27.18 (C-3), 30.16 (C-5),
46.74 (C-7), 60.90 (d, J ϭ 4.18 Hz, C-2), 62.07 (C-6), 67.85 (C-9),
79.83 (C-11), 98.95 (C-10), 119.87 (C-12), 128.39 (d, J ϭ 12.46 Hz,
Ph m-C), 128.96 (d, J ϭ 12.07 Hz, Ph m-C), 130.85 (d, J ϭ
62.07 Hz, Ph i-C), 131.86 (d, J ϭ 49.16 Hz, Ph i-C), 132.42 (Ph m-
C), 132.90 (d, J ϭ 11.39 Hz, Ph o-C), 133.13 (Ph p-C), 134.61 (d,
J ϭ 13.04 Hz, Ph o-C) ppm. 31P NMR (162 MHz, CD2Cl2): δ ϭ
102.90 ppm. ESI: m/z ϭ 1101 [M ϩ Na]ϩ, 1043 [M Ϫ Cl]ϩ.
24: From 19 (200 mg, 0.27 mmol) and [(η4-C7H8)PdCl2] (150 mg,
C6D6): δ ϭ 0.96Ϫ1.12 (m, 4 H, H-8), 1.18Ϫ1.25 (m, 2 H, H-3),
1.62Ϫ1.67 (m, 2 H, H-3), 1.74 (br. s, 2 H, H-4), 2.31Ϫ2.48 (m, 6
H, H-7, H-5), 2.86Ϫ2.93 (m, 4 H, H-6, H-2), 3.12 (ddd, J ϭ 14.02,
J ϭ 6.68, J ϭ 2.01 Hz, 2 H, H-6), 3.77Ϫ3.84 (m, 2 H, H-9),
4.05Ϫ4.12 (m, 2 H, H-9), 5.58 (s, 2 H, H-12), 7.01Ϫ7.05 (m, 4 H,
Ph), 7.09Ϫ7.13(m, 8 H, Ph), 7.60Ϫ7.66 (m, 8 H, Ph) ppm. 13C
NMR (100 MHz, C6D6): δ ϭ 25.22 (C-3), 25.53 (C-8), 28.31 (C-
4), 29.96 (C-5), 48.58 (C-7), 49.63 (C-6), 56.78 (d, J ϭ 6.28 Hz, C-
2), 71.22 (d, J ϭ 18.57 Hz, C-9), 79.94 (C-11), 101.20 (C-10), 119.39
(C-12), 128.37 (d, J ϭ 6.70 Hz, Ph m-C), 128.46 (d, J ϭ 6.55 Hz,
Ph m-C), 129.10 (d, J ϭ 1.80 Hz, Ph p-C), 130.55 (d, J ϭ 11.36 Hz,
Ph o-C), 130.76 (d, J ϭ 11.32 Hz, Ph o-C), 143.63 (d, J ϭ 14.51 Hz,
Ph i-C), 143.82 (d, J ϭ 14.69 Hz, Ph i-C) ppm. 31P NMR
(162 MHz, C6D6): δ ϭ 114.60 ppm. EI: m/z ϭ 722 [M]ϩ, 645 [M
Ϫ C6H5]ϩ, 521 [M Ϫ Ph2PO]ϩ, 201 [Ph2PO]ϩ.
General Procedure for the Preparation of the Platinacycles 21 and
22: A solution of [PtCl2(SMe2)2] in CH2Cl2 (4 mL) was added drop-
wise to a stirred solution of 19 and 20 in CH2Cl2 (5 mL). After
15 minutes, the solvent was removed to give a pale-yellow solid.
Recrystallisation from THF and toluene gave a white solid.
21: From 19 (370 mg, 0.51 mmol) and [PtCl2(SMe2)2] (200 mg,
1
0.55 mmol). M.p. 238Ϫ240 °C. H NMR (400 MHz, CDCl3): δ ϭ
1.44Ϫ1.50 (m, 2 H, H-3), 1.73Ϫ1.77 (m, 4 H, H-8), 1.85Ϫ1.92 (m,
2 H, H-3), 2.01 (br. s, 2 H, H-4), 2.78Ϫ2.83 (m, 2 H, H-6),
2.90Ϫ2.95 (m, 2 H, H-5), 3.05Ϫ3.09 (m, 2 H, H-2), 3.27Ϫ3.29 (m,
2 H, H-7), 3.91Ϫ4.01 (m, 2 H, H-9), 4.56Ϫ4.64 (m, 2 H, H-7), 4.86
0.51 mmol). M.p. 195Ϫ197 °C. C46H48Cl2N2O2P2Pt (988.83). 1H (dd, J ϭ 12.46, J ϭ 10.40 Hz, 2 H, H-6), 5.64 (s, 2 H, H-12),
NMR (400 MHz, CDCl3): δ ϭ 0.86Ϫ0.91 (m, 2 H, H-3), 1.37Ϫ1.44 7.30Ϫ7.35 (m, 4 H, Ph), 7.37Ϫ7.47 (m, 6 H, Ph), 7.50Ϫ7.54 (m, 2
(m, 4 H, H-8), 1.97 (br. s, 2 H, H-4), 2.04Ϫ2.10 (m, 2 H, H-3),
H, Ph), 7.66Ϫ7.71 (m, 4 H, Ph), 7.98Ϫ8.03 (m, 4 H, Ph) ppm. 13C
2.24Ϫ2.32 (m, 2 H, H-7), 2.48Ϫ2.50 (m, 2 H, H-7), 2.71Ϫ2.74 (m, NMR (100 MHz, CDCl3): δ ϭ 25.64 (C-8), 26.16 (C-3), 27.27 (C-
2 H, H-5), 2.86Ϫ2.89 (m, 2 H, H-6), 3.07Ϫ3.11 (m, 2 H, H-2), 3.21 4), 30.02 (C-5), 52.96 (C-6), 54.79 (C-7), 61.02 (C-2), 67.40 (C-9),
(dd, J ϭ 13.22, J ϭ 10.07 Hz, 2 H, H-6), 3.28 (br. s, 2 H, H-9),
3.47Ϫ3.49 (m, 2 H, H-9), 5.88 (s, 2 H, H-12), 7.37Ϫ7.53 (m, 12 H, Ph m-C), 128.61 (d, J ϭ 12.10 Hz, Ph m-C), 131.32 (d, J ϭ
Ph), 7.70Ϫ7.74 (m, 4 H, Ph), 8.04Ϫ8.09 (m, 4 H, Ph), ppm. 13C
78.90 Hz, Ph i-C), 131.85 (d, J ϭ 60.71 Hz, Ph i-C), 132.16 (Ph p-
NMR (100 MHz, CDCl3): δ ϭ 25.57 (C-8), 25.61 (C-3), 26.27 (C- C), 132.68 (d, J ϭ 11.50 Hz, Ph o-C), 132.74 (Ph p-C), 134.30 (d,
80.14 (C-11), 96.91 (C-10), 119.45 (C-12), 128.27 (d, J ϭ 12.50 Hz,
Eur. J. Inorg. Chem. 2004, 749Ϫ761
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
759

M. Fild, C. Thöne, S. Tötös
FULL PAPER
Table 1. Crystal data for the crystal structures of 7, 8, 9, 11, 18 and 21
7
8
9
11
18
21
Formula
Mr
C28H33ClNOPPd
572.37
C28H33ClNOPPd
572.37
C20H34N2O3Pd
456.89
C20H36N2O4Pd
474.91
C22H30N2O2
354.48
C50H56Cl2N2O3P2Pt
1060.90
Habit
yellow prism
yellow prism
yellow prism
yellow block
colourless prism
colourless tablet
Dimensions (mm) 0.46 ϫ 0.22 ϫ 0.16 0.43 ϫ 0.26 ϫ 0.17 0.35 ϫ 0.21 ϫ 0.12 0.38 ϫ 0.37 ϫ 0.27 0.46 ϫ 0.26 ϫ 0.14 0.25 ϫ 0.21 ϫ 0.1
Crystal system
Space group
orthorhombic
P212121
8.7380(14)
16.900(3)
17.208(3)
90
90
90
2541.3(7)
4
1.497
orthorhombic
P212121
8.9083(6)
16.6224(10)
17.1522(10)
90
90
90
2539.9(3)
4
1.497
monoclinic
P21
11.3948(6)
7.3436(4)
12.3835(8)
90
99.917(3)
90
1020.75(10)
2
orthorhombic
P212121
8.4067(14)
10.0958(18)
23.817(4)
90
90
90
2021.4(6)
4
1.560
orthorhombic
P212121
7.7902(9)
10.9628(12)
22.772(2)
90
90
90
1944.8(4)
4
1.211
triclinic
P1
˚
a (A)
11.3323(10)
12.8787(10)
17.6247(14)
92.556(3)
108.556(3)
104.543(3)
2338.6(3)
2
1.507
3.23
1072
Ϫ140
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
3
˚
V (A )
Z
Dx (Mg·mϪ3
)
1.487
0.93
476
Ϫ140
µ (mmϪ1
F(000)
T (°C)
2θmax
)
0.92
1176
Ϫ140
60
0.92
1176
Ϫ140
60
0.95
992
Ϫ140
60
0.08
768
Ϫ140
60
60
60
Transmission
No. of reflections:
measured
independent
Rint
Parameters
Restraints
wR (F2, all refl.)
R (F, Ͼ4σ(F)]
S
0.56Ϫ0.83
0.69Ϫ0.86
0.74Ϫ0.89
0.43Ϫ0.75
no correction
0.59Ϫ0.80
53471
7430
0.0686
299
51018
7423
0.0192
299
18924
5947
0.0177
243
40178
5912
0.0776
260
22535
3225
0.0329
243
48900
25501
0.0322
1031
0
0
1
0
0
952
0.0699
0.0266
1.07
0.0369
0.0139
1.05
0.0397
0.0154
1.04
0.0643
0.0245
1.03
0.0934
0.0342
1.02
0.0763
0.0333
0.98
Max. ∆/σ
Max. ∆ρ (e·A
Ͻ0.001
1.18
0.001
0.48
0.001
0.43
0.001
0.76
0.001
0.25
0.001
2.25
Ϫ3
˚
)
Flack parameter Ϫ0.036(17)
Ϫ0.012(10)
0.011(13)
0.00(2)
0.005(4)
J ϭ 12.97 Hz, Ph o-C) ppm. 31P NMR (162 MHz, CDCl3): δ ϭ
103.76 ppm. ESI: m/z ϭ 1101 [M ϩ Na]ϩ, 1043 [M Ϫ Cl]ϩ.
[1] [1a]
R. Noyori, Asymmetric Catalysis in Organic Synthesis;
[1b]
Wiley: New York, 1994.
I. Ojima, Catalytic Asymmetric
Synthesis; VCH: New York, 1993.
Crystal Structure Analyses: The crystal-structure data for 7, 8, 9,
11, 18 and 21 were collected on a Bruker SMART 1000CCD area
detector (graphite-monochromated Mo-Kα radiation, λ ϭ 71.073
pm) at Ϫ140 °C in the ω- and ϕ-scan mode. Empirical absorption
corrections were applied using the program SADABS. The struc-
tures were solved by direct methods using SHELXS-86/97,[22] and
subjected to full-matrix least-squares refinement on F2 using
SHELXL-93/97,[23] with anisotropic displacement parameters for
non-H atoms. The crystal structure of 21 contains one disordered
THF molecule per formula unit, which could not be resolved satis-
[2] [2a]
´
´
M. Nogradi, Stereoselective Synthesis; VCH: Weinheim,
1995, p. 48ff. [2b] O. Cervinka, Enantioselective Reactions in Or-
ganic Chemistry; Ellis Horwood: New York, 1995, p. 68ff.
ˇ
[3] [3a]
P.-O. Norrby, H. C. Kolb, K. B. Sharpless, J. Am. Chem.
[3b]
Soc. 1994, 116, 8470Ϫ8478.
For a very recent method for
asymmetric desymmetrisation of meso-1,2-diols by phosphinite
derivatives of Cinchona alkaloids see: S. Mizuta, M. Sadamori,
T. Fujimoto, I. Yamamoto, Angew. Chem. 2003, 115,
3505Ϫ3507; Angew. Chem. Int. Ed. 2003, 42, 3383Ϫ3385.
G. D. A. Dijkstra, R. M. Kellog, H. Wynberg, J. S. Svendsen,
I. Marko, K. B. Sharpless, J. Am. Chem. Soc. 1989, 111,
8069Ϫ8076.
E. J. Corey, M. C. Noe, J. Am. Chem. Soc. 1996, 118,
11038Ϫ11053.
[6a] A. Albinati, F. Lianza, H. Berger, P. S. Pregosin, H. Rügger,
[4]
factorily. This led to a residual electron density of 2.25 e·AϪ3. The
˚
crystal structure was therefore refined using the restraints SIMU
and DELU for the carbon, nitrogen and oxygen atoms. Addition-
ally, the restraint FLAT was added to describe the local symmetry
of the phenyl rings. Methyls were treated as rigid groups and O-
bonded hydrogens were refined freely. All other hydrogen atoms
were included using a riding model.
CCDC-216416 (7), -216417 (8), -216418 (9), -216419 (11), -216420
(18) and -216421 (21) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge
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