Noble metal complexes with 4, 4′- and 5, 5′-pyridyl- functionalized (S)-2, 2′-bis(diphenylphosphanyl)-1, 1′-binaphthyl ligands

Article abstract of DOI:10.1002/zaac.201400088

Six metal complexes based on Au^I, Pd^II, or Pt ^II with functionalized (S)-4, 4′- or 5, 5′-bis(3-pyridyl) -2, 2′-bis(diphenylphosphanyl)-1, 1′-binaphthyl ligands (L ¹, L²) have been prepared and fully c

Full text of DOI:10.1002/zaac.201400088

ARTICLE
DOI: 10.1002/zaac.201400088
Noble Metal Complexes with 4,4Ј- and 5,5Ј-Pyridyl-Functionalized (S)-2,2Ј-
Bis(diphenylphosphanyl)-1,1Ј-binaphthyl Ligands
Witri Wahyu Lestari,[a][‡] Peter Lönnecke,[a] and Evamarie Hey-Hawkins*[a]
Keywords: Metal complexes; BINAP; Molecular structure; Gold; Palladium; Platinum
Abstract. Six metal complexes based on AuI, PdII, or PtII with func-
tionalized (S)-4,4Ј- or 5,5Ј-bis(3-pyridyl)-2,2Ј-bis(diphenylphos-
plexes (S)-[Au2Cl2(L1)] (1) and (S)-[Au2Cl2(L2)] (2) show an almost
linear Cl–Au–P arrangement, and the PdII and PtII complexes (S)-
phanyl)-1,1Ј-binaphthyl ligands (L1, L2) have been prepared and fully [PdCl2(L1)] (3), (S)-[PdCl2(L2)] (4), (S)-[PtI2(L1)] (5), and (S)-
characterized. According to single-crystal X-ray analysis, the AuI com-
[PtI2(L2)] (6) exhibit distorted square-planar geometries.
incorporation of homogeneous catalysts to give well-designed
single-site catalysts for shape-, size-, chemo-, or enantioselec-
tive reactions.[17] Compared to zeolites, MOFs are highly tun-
able and can be synthesized under mild reaction conditions.[18]
The use of BINAP derivatives as functionalized linkers to
create enantioselective sites in one-, two-, or three-dimensional
MOFs has hardly been explored; RuII BINAP complexes were
employed as building blocks by Lin and co-workers,[19] and
we have reported several chiral MOFs based on derivatives of
BINAP oxide.[20] Herein, AuI, PdII, and PtII complexes with
4,4Ј- and 5,5Ј-substituted BINAP ligands which are promising
building blocks for chiral MOFs are described.
Introduction
Since the first report by Noyori et al. in 1980,[1] 2,2Ј-bis(di-
phenylphosphanyl)-1,1Ј-binaphthyl (BINAP) derivatives have
been widely explored. Further developments include BINAP
functionalization and complex formation with transition met-
als.[2] BINAP-based metal complexes and BINAP derivatives
also play an important role in homogeneous catalysis.[2,3]
Ruthenium(II),[4,5] rhodium(I),[6] nickel(II),[7] and palladi-
um(II)[8] complexes proved to be efficient catalysts for asym-
metric hydrogenation of α-acylaminoacrylic acids,[9] allylic
alcohols,[5i,10] aldehydes,[5c] and ketones.[5] Chiral RhI-BINAP
complexes can cause a remarkable enantioselective 1,3-
hydrogen shift in allylic amines, converting them to optically
active enamines,[11] which play a key role in the recently estab-
lished industrial synthesis of (–)-menthol.[12] The use of BI-
NAP-based gold(I)[13] and platinum(II)[13e,14] complexes has
also been an attractive topic in enantioselective catalysis. In
addition, the unique features of BINAP ligands[15] provide ad-
vantages in examining transition metal-catalyzed reaction
mechanisms.[16]
Results and Discussion
The ligands (S)-4,4Ј- (L1) and (S)-5,5Ј-bis(3-pyridyl)-2,2Ј-
bis(diphenylphosphanyl)-1,1Ј-binaphthyl (L2) were prepared
by reduction of (S)-4,4Ј- and 5,5Ј-bis(3-pyridyl)-2,2Ј-bis(di-
phenylphosphinoyl)-1,1-binaphthyl,[21] according to a modi-
fied literature procedure.[22] The 31P{1H} NMR spectra
showed a high-field shift from about 28 ppm (BINAP-oxides)
to –15.1 ppm (L1, L2). Colorless crystals of L2 were obtained
from dichloromethane/n-hexane at room temperature. L2 crys-
tallizes in the monoclinic space group P21 with four molecules
in the unit cell (Figure 1).
To date, the targeted synthesis of a desired stereoisomer,
especially in the production of pharmaceuticals, is still domi-
nated by homogeneous chiral catalysts, and only rarely are
heterogeneous catalysts employed. Metal-organic frameworks
(MOFs) offer the possibility to combine the advantages of
heterogeneous and homogeneous catalysts by facilitating the
Reaction of L1 or L2 with [AuCl(tht)] (tht = tetrahydrothio-
phene), [PdCl2(cod)] or [PtI2(cod)] (cod = 1,5-cyclooctadiene)
in dichloromethane overnight at room temperature gave the
corresponding metal complexes (S)-[Au2Cl2(L1)] (1), (S)-
[Au2Cl2(L2)] (2), (S)-[PdCl2(L1)] (3), (S)-[PdCl2(L2)] (4), (S)-
[PtI2(L1)] (5) and (S)-[PtI2(L2)] (6) in good yields after work-
up. All analytical and spectroscopic data are in agreement with
the proposed structures (Scheme 1). The thermal stability of
complexes 1–6 is in the range of 210 to 320 °C.
* Prof. Dr. E. Hey-Hawkins
Fax: +49-341-9739319
E-Mail: hey@rz.uni-leipzig.de
[a] Institut für Anorganische Chemie
Fakultät für Chemie und Mineralogie
Universität Leipzig
Johannisallee 29
04103 Leipzig, Germany
[‡] New address: Department of Chemistry
Sebelas Maret University
The 31P{1H} NMR spectra of 1–6 show singlet signals,
which are shifted downfield (22.9 (1), 21.6 (2), 28.7 (3) and
Surakarta, Jawa Tengah, 57126, Indonesia
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201400088 or from the au-
thor.
28.6 (4), 4.6 (JP,Pt = 3442.5 Hz) (5) and 4.2 ppm (JP,Pt
=
Z. Anorg. Allg. Chem. 2014, 640, (8-9), 1589–1595
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1589

W. W. Lestari, P. Lönnecke, E. Hey-Hawkins
ARTICLE
ecules in the unit cell. Both complexes are located on a crystal-
lographic C2 axis and show an almost linear P–Au–Cl arrange-
ment with bond angles of 175.32(3)° (1) and 175.77(8)° (2)
(Table 1, Figure 2) and Au–P bond lengths of 2.2254(7) (1)
and 2.227(2) Å (2) comparable with those of related AuI phos-
phine complexes.[25] No intra- or intermolecular aurophilic in-
teractions are observed (Au···AuЈ 5.2989(1) (1) and
5.3568(2) Å (2)).[26] Larger dihedral angles between the two
naphthyl rings (88.89(3)° (1) and 84.3(1)° (2) compared to the
free ligands are observed (cf. 77.34(8) and 78.77(7)° in L2).
Table 1. Selected bond lengths /Å and bond angles /° in complexes 1
and 2.
Figure 1. Molecular structure of L2. Both symmetry-independent
molecules in the asymmetric unit are shown (solvent molecules and
hydrogen atoms are omitted and P-phenyl groups are shown in light
gray for clarity, thermal ellipsoids are drawn at 50% probability).
Bond lengths
Au(1)–P(1)
1
2
Bond angles
2.2254(7) 2.227(2) P(1)–Au(1)–Cl(1) 175.32(3) 175.77(8)
118.79(9) 120.0(3)
1
2
Au(1)–Cl(1) 2.2815(7) 2.285(2) C(1)–P(1)–Au(1)
P(1)–C(22)
P(1)–C(16)
P(1)–C(1)
1.801(3) 1.821(7) C(16)–P(1)–Au(1) 113.0(1) 111.8(3)
1.817(3) 1.809(8) C(22)–P(1)–Au(1) 108.1(1) 108.2(2)
1.823(3) 1.832(8) C(12)–N(1)–C(13) 117.5(3) 116.3(8)
3447.7 Hz) (6)) compared to the bis-phosphine ligands
(–15.1 (L1) and –15.1 ppm (L2)). The observed P–Pt coupling
constants are comparable with those reported for similar Pt
complexes of BINAP and BINAP derivatives.[14d,23,24]
Needlelike crystals of (S)-[Au2Cl2(L1)] (1), (S)-
[Au2Cl2(L2)] (2) (colorless, light-sensitive), (S)-[PdCl2(L1)]
(3), (S)-[PdCl2(L2)] (4) (yellow), and (S)-[PtI2(L1)] (5),
(S)-[PtI2(L2)] (6) (orange-brown) suitable for single-crystal
X-ray diffraction analysis were obtained from concentrated
dichloromethane solutions of the metal complexes layered with
n-hexane.
N(1)–C(12) 1.340(4) 1.35(1) N(1)–C(12)–C(11) 123.6(3) 124.5(8)
N(1)–C(13) 1.345(4) 1.35(1) N(1)–C(13)–C(14) 123.5(3) 122.9(9)
Palladium(II) and Platinum(II) Complexes: (S)-[PdCl2(L1)]
(3), (S)-[PdCl2(L2)] (4), (S)-[PtI2(L1)] (5), and (S)-[PtI2(L2)]
(6)
Compound 3 crystallizes as twinned crystals with a twin
domain ratio of 0.881(1):0.119(1) in the tetragonal space group
P43, 4 in the orthorhombic space group P21212, and both have
four molecules in the unit cell. Compound 5 crystallizes in the
tetragonal space group P43212 and 6 in the orthorhombic space
group P21212, both with four molecules in the unit cell. The
Gold(I) Complexes (S)-[Au2Cl2(L1)] (1) and (S)-
[Au2Cl2(L2)] (2)
Compound 1 crystallizes in the orthorhombic space group molecule of complex 5 is located on a crystallographic C2 axis.
P21212 and 2 in the monoclinic space group C2, with two mol- In 3–6, the PdII and PtII atoms are coordinated in a square-
Scheme 1. Formation of AuI, PdII, and PtII complexes of L1 and L2.
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Z. Anorg. Allg. Chem. 2014, 1589–1595

Metal Complexes with (S)-2,2Ј-Bis(diphenylphosphanyl)-1,1Ј-binaphthyl Ligands
(2.252(2)–2.260(1) Å), Pd–Cl (2.339(2)–2.354(2) Å), Pt–P
(2.249(2)–2.253(2) Å], and Pt–I (2.6327(6)–2.6561(4) Å) bond
lengths are in the ranges observed for related PdII BINAP[27]
and BINAP-based PtI2 complexes.[24] In contrast to 1 and 2,
Table 3. Selected bond lengths /Å and bond angles /° in complexes 5
and 6.
Bond
5
6
Bond angles
5
6
lengths
Pt(1)–P(1) 2.253(1) 2.253(2) P(1)Ј–Pt(1)–P(1) 92.99(6)
–
Pt(1)–P(2)
Pt(1)–I(1)
Pt(1)–I(1)Ј 2.6561(4)
Pt(1)–I(2)
P(1)–C(1)
–
2.249(2) P(2)–Pt(1)–P(1)
2.6561(4) 2.6327(6) P(1)Ј–Pt(1)–I(1) 162.73(3)
P(1)Ј–Pt(1)–I(1)Ј 91.50(3)
2.6502(5) P(2)–Pt(1)–I(1)
1.857(4) 1.839(7) P(1)–Pt(1)–I(1)
–
91.83(6)
–
–
–
–
–
164.07(5)
91.50(3) 92.04(5)
P(1)–C(16) 1.806(5)
P(1)–C(22) 1.817(4)
N(1)–C(12) 1.338(6)
N(1)–C(13) 1.312(8)
–
–
–
–
P(1)–Pt(1)–I(1)Ј 162.73(3)
–
–
I(1)–Pt(1)–I(1)Ј
P(2)–Pt(1)–I(2)
P(1)–Pt(1)–I(2)
89.11(2)
–
–
–
91.97(4)
163.42(4)
88.70(2)
P(1)–C(31)
P(1)–C(37)
P(2)–C(43)
P(2)–C(49)
N(1)–C(22)
N(1)–C(23)
N(2)–C(27)
N(2)–C(28)
–
–
–
–
–
–
–
–
1.824(7) I(1)–Pt(1)–I(2)
1.813(6) C(1)–P(1)–Pt(1) 111.7(1) 108.8(2)
1.830(6) C(16)–P(1)–Pt(1) 114.1(1)
1.816(7) C(22)–P(1)–Pt(1) 111.1(2)
1.35(1)
1.28(2)
1.40(2)
1.38(3)
–
–
–
C(31)–P(1)–Pt(1)
C(37)–P(1)–Pt(1)
C(11)–P(2)–Pt(1)
C(43)–P(2)–Pt(1)
C(49)–P(2)–Pt(1)
–
–
–
–
–
112.1(2)
117.5(2)
111.3(2)
113.5(2)
117.1(2)
Symmetry transformations used to generate equivalent atoms: (Ј) =
–y + 1, –x + 1, –z + 1/2.
Figure 2. Molecular structures of 1 (top) and 2 (bottom). Hydrogen
atoms are omitted and P-phenyl groups are shown in light gray for
clarity (thermal ellipsoids are drawn at 50% probability). Symmetry
transformations used to generate equivalent atoms: –x + 2, –y + 2, z
(for 1); –x, y, –z (for 2).
planar fashion by a chelating BINAP and two chlorido (3, 4)
or iodido (5, 6) ligands (dihedral angles between the Cl(1)–
Pd–Cl(2) and P(1)–Pd–P(2) planes are 21.5 (3) and 21.6° (4),
and those between I–Pt–I and P–Pt–P are 24.1 (5) and 22.9°
(6)) with P–M–P and X–M–X (X = Cl, M = Pd; X = I, M =
Pd) bond angles close to 90° (range 88.70(2)–92.99(6)°) and
P–M–Xtrans bond angles ranging from 162.73(3) to 165.97(6)°
(see Table 2 and Table 3, Figure 3 and Figure 4). The Pd–P
Table 2. Selected bond lengths /Å and bond angles /° in complexes 3
and 4.
Bond
3
4
Bond angles
3
4
lengths
Pd(1)–P(1) 2.257(2) 2.252(2) P(1)–Pd(1)–P(2)
Pd(1)–P(2) 2.260(1) 2.255(2) P(1)–Pd(1)–Cl(1)
Pd(1)–Cl(1) 2.339(2) 2.346(2) P(2)–Pd(1)–Cl(1)
Pd(1)–Cl(2) 2.349(2) 2.354(2) P(1)–Pd(1)–Cl(2)
P(1)–C(37) 1.790(6) 1.794(8) P(2)–Pd(1)–Cl(2)
92.89(5) 92.10(9)
89.23(7) 88.38(8)
163.22(7) 163.43(9)
165.97(6) 165.39(9)
90.77(6) 92.49(8)
P(1)–C(1)
1.842(5) 1.825(8) Cl(1)–Pd(1)–Cl(2) 91.16(8) 91.15(8)
P(2)–C(11) 1.846(5) 1.850(8) C(1)–P(1)–Pd(1)
P(2)–C(49) 1.809(5) 1.812(9) C(37)–P(1)–C(1)
N(1)–C(23) 1.312(8) 1.32(1) C(31)–P(1)–C(1)
111.4(2)
110.4(2) 108.1(4)
103.4(2) 110.6(4)
112.7(3)
N(1)–C(22) 1.343(7) 1.34(1) C(37)–P(1)–Pd(1) 112.1(2) 115.6(3)
N(2)–C(28) 1.316(9) 1.30(2) C(23)–N(1)–C(22) 115.8(6) 115(1)
N(2)–C(27) 1.334(7) 1.35(2) C(28)–N(2)–C(27) 115.8(6) 119(2)
Figure 3. Molecular structures of 3 (top) and 4 (bottom). Hydrogen
atoms are omitted and P-phenyl groups are shown in light gray for
clarity. Thermal ellipsoids are drawn at 30% probability.
Z. Anorg. Allg. Chem. 2014, 1589–1595
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W. W. Lestari, P. Lönnecke, E. Hey-Hawkins
ARTICLE
by repeated evacuation and purging with nitrogen before use. CDCl3
was dried with LiAlH4, distilled and kept over molecular sieves.
[Pd(PPh3)4],[28] [AuCl(tht)],[29] [PdCl2(cod)],[30] [PtI2(cod)],[30,31] (S)-
4,4Ј- and 5,5Ј-bis(3-pyridyl)-2,2Ј-bis(diphenylphosphinoyl)-1,1-bi-
naphthyl[21] were synthesized according to literature procedures.
[Ti(OiPr4)], tetramethyldisiloxane (TMDS) and trichlorosilane
(HSiCl3) were used as purchased under inert conditions. Infrared spec-
tra were recorded on a Perkin–Elmer Spectrum 2000 FT-IR spectrome-
similar (3, 5) or smaller (4, 6) dihedral angles between the two
naphthyl rings are observed in complexes 3–6 (78.2(9) (3),
76.1(2) (4), 79.0(1) (5), and 72.8(1)° (6)) in comparison with
the free ligand L2 (77.34(8) and 78.77(7)°).
1
ter by using KBr disks. The H, 13C, and 31P NMR spectra were re-
corded with a Bruker AVANCE DRX 400 spectrometer; chemical
shifts are given in parts per million (ppm) at 400.13, 100.63, and
161.98 MHz, respectively. Internal standards were tetramethylsilane
for 1H and 13C NMR, and external 85% H3PO4 for 31P NMR spec-
troscopy. Mass spectra were recorded with an FT-ICR-MS Bruker Dal-
tonics ESI mass spectrometer (APEX 11.7 Tesla). Elemental analyses
were obtained with a VARIO EL (Heraeus) microanalyzer. The melting
points were determined in sealed capillaries with a Gallenkamp instru-
ment.
X-ray Crystallography: The X-ray data were collected with a Gem-
ini-S CCD diffractometer (Agilent Technologies) by using Mo-Kα radi-
ation and omega scan rotation. Data collection and data reduction were
done with CrysAlis Pro including the program SCALE3 ABSPACK
for empirical absorption correction.[32] The structures of L2 and 1 were
solved by direct methods, and those of 2–6 by Patterson methods using
the program SHELXS-86 (2) or SHELXS-97 (all other structures).[33]
Anisotropic refinement of all non-hydrogen atoms with SHELXL-
97[33] with the exception of disordered parts of the structures.
Hydrogen atoms of all structures were calculated on idealized positions
by using the riding model. The crystals of L2 and 3 were found to be
twinned. Twin law by rows for both compounds: 1 0 0; 0 –1 0;
0
0
–1, twin domain ratio: 0.814(2):0.186(2) (for L2) and
0.881(1):0.119(1) (for 3). Fundamental structure parameters are given
in Table 4. Structure figures were generated with ORTEP[34] and Dia-
mond-3.[35] CCDC-975448 (L2), -975449 (1), -975450 (2), -975451
(3), -975452 (4), -975453 (5) and -975454 (6) contain the supplemen-
tary crystallographic data for this paper. The data can be obtained free
of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; Fax: (+44)1223-336-033; or deposit@ccdc.cam.uk).
Figure 4. Molecular structures of 5 (top) and 6 (bottom). Hydrogen
atoms are omitted and P-phenyl groups are shown in light gray for
clarity. Thermal ellipsoids are drawn at 30% probability. Symmetry
transformations used to generate equivalent atoms in 5: (Ј) = –x + 1,
–y + 1, –z + 1/2.
Preparation of L1 and L2: The corresponding phosphine oxide[21] of
L1 or L2 (2.04 g, 2.52 mmol, 1 equiv.) and Na2SO4 as drying agent
(10 wt.-%, 0.204 g) were suspended in dry toluene (50 mL) and TMDS
(2.23 mL, 12.6 mmol, 5 equiv.) and [Ti(OiPr4)] as catalyst (0.2 mL,
0.505 mmol, 0.2 equiv.) were added. The mixture was stirred and
heated at 90 °C for 48 h. The mixture was cooled to 0 °C, the solid
product isolated by filtration, washed 4–5 times with cold n-pentane
(5 mL) and twice with cold methanol (5 mL) and the resulting beige-
Conclusions
Complexes based on AuI, PdII, or PtII and functionalized
(S)-binaphthyl ligands have been developed for further use as
(potentially catalytically active) chiral building blocks in the
construction of MOFs. The gold(I) complexes show an almost
linear Cl–Au–P arrangement, and the palladium(II) and plati-
num(II) complexes exhibit distorted square-planar geometries. white solid dried in vacuo. Yield L1: 90% (1.76 g). M.p. Ͼ260 °C
Future work will now focus on catalytic tests with 1–6 and on
(decomp.). ESI-MS (m/z): 777.3 [M + H]+ (calcd. for C54H38N2P2:
1
776.84 g mol–1). H NMR (CDCl3): δ = 6.90–6.96 (m, 4 H, pyridyl),
the synthesis of MOFs from these building blocks by em-
ploying the pyridyl moieties as donor groups for CdII, CuI,
7.01–7.08 (m 20 H, phenyl), 7.28–7.35 (m, 6 H, naphthyl), 7.75–7.80
(m, 4 H, naphthyl), 8.58 (d, J = 3.08 Hz, 2 H, pyridyl), 8.68 (s, 2 H,
CuII, etc.
pyridyl). 13C{1H} NMR (CDCl3): δ = 123.1 (s), 125.1 (s), 126.0 (s),
127.1 (s), 127.7 (s), 128.0 (s), 128.6 (s), 131.3 (s), 131.8 (s), 132.5 (s),
132.6 (s), 132.7 (s), 133.6 (t, J = 5.1 Hz), 134.0 (s), 134.1 (s), 134.2
Experimental Section
(s), 136.1 (s), 136.3 (s), 137.4 (s), 145.4 (t, J = 20.5 Hz), 148.5 (s),
General Methods: All reactions were carried out under nitrogen atmo-
sphere by using standard Schlenk techniques. Solvents were purified 3428 (br., N···H), 3051 (m, C–H aryl), 2964 (s), 1585 (w), 1546 (w),
150.8 (s). 31P{1H} NMR (CDCl3): δ = –15.1 (s, PPh2). IR (KBr): ν˜ =
with an MBRAUN Solvent Purification System SPS-800 Series. Tri-
ethylamine was dried with CaH2, distilled and kept under nitrogen over
molecular sieves (3 Å). THF and o-xylene were dried with sodium,
1506 (m), 1475 (s), 1435 (s, P–C6H5), 1415 (s), 1338 (m), 1262 (s),
1093 (m), 1025 (s, C–N), 974 (w), 869 (w), 810 (s), 768 (m), 743 (s,
C–H), 716 (m), 696 (s, P–C), 523.96 (m) cm–1. C54H38N2P2 (776.84):
distilled and stored under nitrogen. 30% aq. NaOH was deoxygenated C, 83.49; H, 4.93; N, 3.61. Found: C, 82.25; H, 4.95; N, 3.20.
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Metal Complexes with (S)-2,2Ј-Bis(diphenylphosphanyl)-1,1Ј-binaphthyl Ligands
Table 4. Crystallographic data for L2 and complexes 1–6.
L2·CH2Cl2
1·2CH2Cl2
2·5CH2Cl2
3·2CH2Cl2
4·2.5CH2Cl2
5·2CH2Cl2
6·CH2Cl2
Formula
FW
Temp. /K
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
C55H40Cl2N2P2 C56H42Au2Cl6N2P2 C59H48Au2Cl12N2P2 C56H42Cl6N2P2Pd C56.50H43Cl7N2P2Pd C56H42Cl4I2N2P2Pt C55H40Cl2I2N2P2Pt
861.73
130(2)
Monoclinic
P21
1411.49
130(2)
Orthorhombic
P21212
14.9679(2)
18.5949(2)
8.9097(2)
90
1666.27
130(2)
Monoclinic
C2
1123.96
230(2)†
Tetragonal
P43
1166.42
130(2)
Orthorhombic
P21212
17.1366(5)
30.5012(9)
9.7792(2)
90
1395.55
130(2)
Tetragonal
P43212
14.8905(1)
14.8905(1)
23.0177(3)
90
1310.62
130(2)
Orthorhombic
P212121
9.7672(1)
12.2708(2)
39.1516(9)
90
17.9813(4)
12.7306(2)
18.9611(5)
90
26.308(1)
8.7391(2)
13.6879(4)
90
14.8471(2)
14.8471(2)
22.7468(6)
90
β /°
γ /°
V /Å3
90.458(2)
90
4340.3(2)
4
1.319
1792
90
90
104.709(4)
90
3043.8(2)
2
1.818
1616
90
90
5014.2(2)
4
1.489
90
90
5111.5(2)
4
1.516
90
90
90
90
4692.4(1)
4
1.855
2479.81(7)
2
1.890
1364
43112
5103.65(8)
4
1.816
2696
64005
Z
Dc /Mg·m–3
F(000)
Reflns
2280
30929
2364
56874
2528
40479
44735
15905
collected
Independent
reflns
15318
7586
9288
10258
10454
7794
9585
Rint
0.0512
1.022
0.0431
1.067
0.0375
1.035
0.0516, 0.1161
0.0490
1.037
0.0439, 0.0929
0.0780
1.192
0.0781, 0.1587
0.0532
1.071
0.0360, 0.0677
0.0419
1.096
0.0379, 0.0798
GOF on F2
R1, wR2
[I Ͼ 2σ(I)]
0.0632, 0.1511 0.0227, 0.0416
R1, wR2 (all data) 0.0862,
0.0263, 0.0427
–0.017(3)
0.0645, 0.1238
–0.006(9)
0.0620, 0.1037
–0.06(3)
0.0990,0.1670
–0.02(6)
0.0458, 0.0719
–0.009(5)
0.0424, 0.0819
–0.001(6)
0.1688
Flack parameter
0.00(3)
†: At 130 K, most reflections are split up.
Yield L2: 93% (1.82 g). M.p. Ͼ240 °C (decomp.). ESI-MS (m/z):
pyridyl), 8.73 (br., 2 H, pyridyl). 13C{1H} NMR (CDCl3): δ = 123.4
777.3 [M + H]+ (calcd. for C54H38N2P2: 776.84 g mol–1). 1H NMR (s), 125.6 (s), 126.2 (s), 126.4 (s), 126.9 (s), 127.1 (s), 127.5 (s), 127.6
(CDCl3): δ = 6.92–7.00 (m, 4 H, pyridyl), 7.05–7.18 (m, 20 H, phenyl), (s), 129.0 (s), 129.1 (s), 129.2 (s), 129.9 (s), 130.5 (s), 131.0 (d, J =
7.29 (d, J = 6.8 Hz, 2 H, naphthyl), 7.42–7.44 (m, 4 H, naphthyl),
4.9 Hz), 131.6 (d, J = 6.75 Hz), 133.1 (s), 133.9 (d, J = 14.1 Hz), 134.1
7.87–7.90 (m, 4 H, naphthyl), 8.68 (d, J = 3.64 Hz, 2 H, pyridyl), 8.8 (s), 134.2 (s), 134.5 (d, J = 13.8 Hz), 135.1 (s), 138.8 (s), 139.1 (d, J
(s, 2 H, pyridyl). 13C{1H} NMR (CDCl3): δ = 123.0 (s), 125.3 (s), = 8.4 Hz), 143.3 (dd, J = 7.5; 7.8 Hz), 149.1 (s), 150.5 (s). 31P{1H}
125.5 (s), 127.8 (s), 127.9 (s), 128.0 (s), 128.08 (s), 128.13 (s), 128.6 NMR (CDCl3): δ = 22.9 (s, PPh2). IR (KBr): ν˜ = 3441 (br., C–N···H),
(s), 131.1 (s), 131.3 (s), 132.9 (s), 133.6 (t, J = 4.97 Hz), 134.3 (s), 3049 (w, C–H aryl), 2963 (m), 1631 (w), 1506 (w), 1479 (m), 1436
136.1 (s), 136.2 (s), 136.4 (s), 137.0 (s), 137.4 (s), 137.5 (s), 145.2 (t,
J = 20.2 Hz), 148.6 (s), 150.7 (s). 31P{1H} NMR (CDCl3): δ = –15.1
(s, PPh2). IR (KBr): ν˜ = 3457 (br., N···H), 2964 (s), 1653 (w), 1631
(w), 1475 (m), 1433 (m, P–C6H5), 1263 (s), 1096 (s), 1023 (s, C–N),
868 (w), 803 (s), 743 (m, C–H), 696 (w, P–C), 503 (w) cm–1.
C54H38N2P2 (776.84): C, 83.49; H, 4.93; N, 3.61. Found: C, 82.50; H,
5.01; N, 3.49.
(s, P–C6H5), 1262 (s), 1098 (s), 804 (s), 744 (m, C–H), 715 (m), 692
(s, P–C), 616 (m), 540 (m, C–H), 494 (m) cm–1. C54H38Au2Cl2N2P2
(1241.68): C, 52.23; H, 3.08; N, 2.26. Found: C, 50.78; H, 3.11; N,
2.03.
2: Yield: 89% (0.1 g). M.p.Ͼ 290 °C (decomp.). ESI-MS (m/z):
1205.1 [M–Cl+H]+ (calcd. for C54H38Au2Cl2N2P2: 1241.68 g mol–1).
1H NMR (CDCl3): δ = 7.02–7.17 10 (m, 4 H, pyridyl), 7.16–7.34 (m,
20 H, phenyl), 7.39–7.44 (m, 4 H, naphthyl), 7.50–7.52 (m, 4 H, naph-
thyl), 8.11 (d, J = 8.8 Hz, 2 H, pyridyl), 8.66 (d, J = 3.6 Hz, 2 H,
pyridyl), 8.8 (br., 2 H, pyridyl). 13C{1H} NMR (CDCl3): δ = 123.7
General Procedure for Complexes 1 and 2
A solution of L1 or L2 (0.07 g, 0.09 mmol) in CH2Cl2 (7 mL) was (s), 125.7 (s), 126.1 (s), 126.7 (s), 127.0 (s), 127.2 (s), 127.7 (s), 127.8
added slowly to a dichloromethane solution (5 mL) of [AuCl(tht)]
(0.064 g, 0.2 mmol) covered with aluminum foil. After stirring over-
(s), 128.97 (s), 129.1 (s), 129.2 (s), 129.5 (s), 130.2 (s), 130.48 (d, J
= 4.24 Hz), 130.9 (s), 131.4 (s), 131.5 (s), 131.6 (s), 133.1 (s), 133.2
night at room temperature, the solvent was evaporated to ca. 4 mL and (s), 133.3 (s), 134.4 (s), 134.5 (s), 134.7 (s), 136.1 (s), 137.0 (s), 143.9
the solution was filtered. The concentrated solution was layered slowly (s), 147.7 (s), 149 (s). 31P{1H} NMR (CDCl3): δ = 21.6 (s, PPh2). IR
with n-hexane (ratio 1:1 or 1:2 (dichloromethane:n-hexane)), which (KBr): ν˜ = 3448 (br., C–N···H), 3054 (w, C–H aryl), 2963 (s, C–H),
led to the formation of needlelike colorless crystals after standing at
room temp. overnight.
1635 (w), 1479 (m), 1436 (s, P–C6H5), 1412 (w), 1262 (s), 1098 (s),
1023 (s, C–N), 803 (s), 751 (s, C–H), 696 (s, P–C), 654 (w), 617 (w),
546 (m, C–H), 512 (w) cm–1. C54H38Au2Cl2N2P2 (1241.68): C, 52.23;
H, 3.08; N, 2.26. Found: C 50.77; H 3.26; N 2.47.
1: Yield: 89% (0.1 g). M.p. Ͼ210 °C (decomp). ESI-MS (m/z): 1205.1
[M–Cl+H]+ (calcd. for C54H38Au2Cl2N2P2: 1241.68 g mol–1). 1H
NMR (CDCl3): δ = 6.86–6.88 (m, 2 H, pyridyl), 6.92–6.96 (m, 2 H,
pyridyl), 7.12–7.24 (m, 12 H, phenyl), 7.27–7.43 (m, 10 H, phenyl,
naphthyl), 7.52 (dd, J = 7.76; 7.48 Hz, 4 H, binaphthyl), 7.88 (d, J = A dichloromethane solution (7 mL) of L1 or L2 (0.07 g, 0.09 mmol)
8.4 Hz, 2 H, naphthyl), 8.20 (br., 2 H), 8.60 (d, J = 4.3 Hz, 2 H, was added slowly to dichloromethane solution (7 mL) of
General Procedure for Complexes 3–6
a
Z. Anorg. Allg. Chem. 2014, 1589–1595
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1593

W. W. Lestari, P. Lönnecke, E. Hey-Hawkins
[PdCl2(cod)] (0.027 g, 0.09 mmol) or [PtI2(cod)] (0.043 g, 0.09 mmol). 1498 (w), 1478 (s), 1436 (s, P–C6H5), 1262 (s), 1099 (s), 1025 (s, C–
ARTICLE
After stirring overnight at room temp. the solvent was evaporated to
ca. 4 mL and the solution was filtered. The concentrated solution was
layered slowly with n-hexane (in a ratio of 1:1 or 1:2), which led to
the formation of needlelike yellow crystals (3, 4) and orange-brown
crystals (5 and 6) after three to seven days standing at room temp. The
obtained crystals were suitable for single-crystal X-ray measurements.
N), 806 (s), 748 (m, C–H), 711 (m), 695 (s, P–C), 650 (m), 568 (s,
C–H), 510 (s) cm–1. C54H38I2N2P2Pt (1225.73): C, 52.91; H, 3.12; N,
2.29. Found: C, 52.30; H, 3.28; N, 1.99.
Supporting Information (see footnote on the first page of this article):
X-ray crystallographic data and cif files, alternative synthesis for L1
and L2, and hydrogen bonding observed in complex 3.
3: Yield: 96% (0.082 g). M.p. 318–320 °C (decomp.). ESI-MS (m/z):
917.2 [M–Cl+H]+ (calcd. for C54H38Cl2N2P2Pd: 954.17 g mol–1). 1H
NMR (CDCl3): δ = 6.87–6.90 (m, 2 H, pyridyl), 7.00 (d, J = 8.5 Hz,
2 H, pyridyl), 7.18–7.23 (m, 8 H, phenyl), 7.30–7.42 (m, 14 H, phenyl,
naphthyl), 7.51–7.55 (m, 4 H, naphthyl), 7.76–7.81 (m, 4 H), 8.46 (s,
H, pyridyl), 8.66 (d, J = 3.96 Hz, 2 H, pyridyl). 13C{1H} NMR
(CDCl3): δ = 123.6 (s), 125.6 (s), 127.2 (s), 127.4 (s), 127.5 (s), 127.7
(s), 127.8 (s), 128.6 (s), 128.7 (s), 129.0 (s), 129.6 (s), 130.7 (s), 131.3
(s), 131.9 (s), 133.5 (d, J = 7.5 Hz), 134.8 (s), 135.0 (s), 135.1 (s),
136.9 (s), 149.3 (s), 150.0 (s). 31P{1H} NMR (CDCl3): δ = 28.7 (s,
PPh2). IR (KBr): ν˜ = 3433 (br., C–N···H), 2962 (m, C–H aryl), 1634
(w), 1437 (s, P–C6H5), 1262 (s), 1099 (s), 804 (s), 747 (w, C–H), 697
(m, P–C), 617 (w), 505 (w) cm–1. C54H38Cl2N2P2Pd (954.17): C,
67.97; H, 4.01; N, 2.94. Found: C, 66.70; H, 3.84; N, 2.67.
Acknowledgments
This work was supported by the Faculty for the Future (FFTF)
Schlumberger Foundation (doctoral fellowship for W.W.L). Support
from the EU COST Action CM0802 PhoSciNet is gratefully
acknowledged. We thank Chemetall GmbH and BASF SE for generous
donations of chemicals.
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(w), 1479 (s), 1436 (s, P–C6H5), 1310 (w), 1261 (s), 1191 (w), 1098
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1098.1 [M–I+H]+ (calcd. for C54H38I2N2P2Pt: 1225.73 g mol–1). 1H
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phenyl), 7.29–7.40 (m, 16 H, phenyl), 7.52–7.56 (m, 4 H, naphthyl),
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1504 (m), 1478 (s), 1436 (s, P–C6H5), 1262 (s), 1099 (s), 802 (s), 741
(s, C–H), 716 (s), 695 (s, P–C), 560 (m), 538 (s, C–H), 525 (s), 502
(s) cm–1. C54H38I2N2P2Pt (1225.73): C, 52.91; H, 3.12; N, 2.29. Found:
C, 50.83; H, 3.09, N, 2.04.
6: Yield: 98% (0.11 g). M.p. 274–275 °C (decomp.). ESI-MS (m/z):
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NMR (CDCl3): δ = 6.76–6.78 (m, 2 H, pyridyl), 6.87–7.00 (m, 2 H,
pyridyl), 7.12–7.19 (m, 6 H, phenyl), 7.29–7.45 (m, 16 H, phenyl,
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(s), 129.0 (s), 130.0 (s), 131.0 (s), 131.7 (s), 133.3 (s), 135.4 (s), 135.5
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ν˜ = 3447 (br., C–N···H), 3044 (w, C–H aryl), 2962 (m), 1587 (m),
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Received: February 24, 2014
Published Online: April 7, 2014
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