(Iminophosphoranyl)(thiophosphoranyl)methanide {CH(PPh 2NSiMe3)(Ph2PS)}- as a ligand in rare-earth-element chemistry

Article abstract of DOI:10.1021/om400001e

The (iminophosphoranyl)(thiophosphoranyl)methanide {CH(PPh ₂=NSiMe₃)(PPh₂=S)}^- has been introduced as a ligand into the chemistry of yttrium and the lanthanides. First, the bimetallic potassium reagent [K{CH(PPh₂=NSiMe ₃)(PPh₂=S)}]₂ was synthesized by deprotonation of [CH₂(PPh₂=NSiMe₃)(PPh₂=S)] with KH. [K{CH(PPh₂=NSiMe₃)(PPh₂=S)}]₂ forms a dimeric structure in the solid state. The potassium atoms are bridged by the sulfur atom of the ligand. Moreover, an η⁶ coordination of one phenyl ring is observed. The salt metathesis of [K{CH(PPh ₂=NSiMe₃)(PPh₂=S)}]₂ with LnCl ₃ led to the dichloro complexes [{CH(PPh₂=NSiMe ₃)(PPh₂=S)}LnCl₂(THF)] (Ln = Dy, Er). The bis(amido) compounds [{CH(PPh₂=NSiMe₃)(PPh ₂=S)}Ln{N(SiHMe₂)₂}₂] (Ln = Y, Sm, Er, Lu) were obtained by amine elimination from [CH₂(PPh ₂=NSiMe₃)(PPh₂=S)] and [Ln{N(SiHMe ₂)₂}₃(THF)₂]. The amido complex [{CH(PPh₂=NSiMe₃)(PPh₂=S)}Er{N(SiHMe ₂)₂}₂] could also be accessed by the reaction of [{CH(PPh₂=NSiMe₃)(PPh₂=S)}ErCl ₂(THF)] with KN(SiHMe₂)₂.

Full text of DOI:10.1021/om400001e

Article
pubs.acs.org/Organometallics
(Iminophosphoranyl)(thiophosphoranyl)methanide
{CH(PPh2NSiMe3)(Ph2PS)}− as a Ligand in Rare-Earth-Element
Chemistry
Balasubramanian Murugesapandian,† Magdalena Kuzdrowska, Michael T. Gamer, Larissa Hartenstein,
and Peter W. Roesky*
Institut fur Anorganische Chemie, Karlsruher Institut fur Technologie (KIT), Engesserstrasse 15, 76131 Karlsruhe, Germany
̈
̈
S
* Supporting Information
ABSTRACT: The (iminophosphoranyl)(thiophosphoranyl)methanide {CH(PPh2NSiMe3)-
(PPh2S)}− has been introduced as a ligand into the chemistry of yttrium and the lanthanides.
First, the bimetallic potassium reagent [K{CH(PPh2NSiMe3)(PPh2S)}]2 was synthesized
by deprotonation of [CH2(PPh2NSiMe3)(PPh2S)] with KH. [K{CH(PPh2NSiMe3)-
(PPh2S)}]2 forms a dimeric structure in the solid state. The potassium atoms are bridged by
the sulfur atom of the ligand. Moreover, an η6 coordination of one phenyl ring is observed. The
salt metathesis of [K{CH(PPh2NSiMe3)(PPh2S)}]2 with LnCl3 led to the dichloro
complexes [{CH(PPh2NSiMe3)(PPh2S)}LnCl2(THF)] (Ln = Dy, Er). The bis(amido)
compounds [{CH(PPh2NSiMe3)(PPh2S)}Ln{N(SiHMe2)2}2] (Ln = Y, Sm, Er, Lu) were
obtained by amine elimination from [CH2(PPh2NSiMe3)(PPh2S)] and [Ln{N-
(SiHMe2)2}3(THF)2]. The amido complex [{CH(PPh2NSiMe3)(PPh2S)}Er{N-
(SiHMe2)2}2] could also be accessed by the reaction of [{CH(PPh2NSiMe3)(PPh2
S)}ErCl2(THF)] with KN(SiHMe2)2.
were used as catalysts for hydroamination/cyclization, hydro-
INTRODUCTION
■
silylation, and sequential hydroamination/hydrosilylation re-
Bis(phosphinimino)methanes [CH2(PPh2NR)2] (R =
SiMe3, aryl), are bidentate P−N ligands that have attracted a
number of researchers in the last decades.1 In general,
bis(phosphinimino)methanes can be easily accessed; e.g.,
CH2(PPh2NSiMe3)2 can be obtained in a solvent-free
Staudinger reaction from commercially available starting
materials in a few hours.2 Bis(phosphinimino)methanes can
be deprotonated to give the monoanionic {CH(PPh2NR)2}−
bis(phosphinimino)methanide and dianionic {C(PPh2
NR)2}2− bis(phosphinimino)methandiide ligands.3−5 Both
ligands have been extensively used in main-group,3−14
transition-metal,15−33 and f-element7,17,34−47 chemistry.1 In
most of the solid-state structures reported in the literature,
the monoanionic {CH(PPh2NR)2}− bis(phosphinimino)-
methanide species tends to show a conformation in which, in
addition to the two nitrogen atoms, the methine carbon atom
also coordinates via a long interaction onto the metal atom.
Thus, the six-membered metallacycle (N−P−C−P−N−M),
which is formed by chelation of the two imine groups to the
metal center, adopts a pseudo-boat conformation.34
actions.42
By combining a hard and a soft donor, we also introduced
the monoanionic phosphine(phosphinimino)methanide ligand
{Ph2PCH(PPh2NSiMe3)}− into organometallic chemistry.48
The related ligand systems (Ph2PCHPPh2NR) (R = pMe-
benzyl, p-MeO-benzyl, Ph, nBu, (R)-(+)-Me-benzyl) were
reported by LeFloch.49 Recently, we have focused on the
(iminophosphoranyl)(thiophosphoranyl)methanide ligand
{CH(PPh2NR)(Ph2PS)}−, which is isoelectronic with the
bis(phosphinimino)methanide ligand. Although the aromatic
derivative of (N-aryliminophosphoranyl)(thiophosphoranyl)-
methanes CH2(PPh2NAr)(Ph2PS) (Ar = p-tolyl, p-tolyl) as
well as some platinum compounds were reported by Elsevier,
the isolation of the lithium derivative failed.50 Lately, Cadierno
and Gimeno have reported on the aromatic derivatives
CH2(PPh2NAr)(Ph2PS) (Ar = 2,4,6-C6H2Me3, 4-
C6F4CHO, 4-C6F4CN, 4-C5F4N), which were deprotonated
in situ with nBuLi and then coordinated as monoanionic
ligands {CH(PPh2NAr)(Ph2PS)}− to ruthenium.51 Recently,
So and co-workers reported {CH2(PPh2NSiMe3)(PPh2
S)} obtained by the reaction of the {Ph2PCH2(PPh2
NSiMe3)} with sulfur in refluxing toluene.52 Deprotonation
of {CH2(PPh2NSiMe3)(PPh2S)} with nBuLi gave the
For about a decade we have studied the bis(phosphinimino)-
methanide {CH(PPh2NSiMe3)2}− as a ligand for the
replacement of cyclopentadienyl in rare-earth-metal chemis-
try.7,34−47 Upon further derivatization we have discovered
various catalysts for the polymerization of polar monomers and
for σ-bond metathesis reactions: e.g., the amido complexes
[{CH(PPh2NSiMe3)2}Ln{N(SiHMe2)2}2] (Ln = Y, La, Sm,
Ho, Lu), which were synthesized via three different pathways,
Special Issue: Recent Advances in Organo-f-Element Chemistry
Received: January 2, 2013
Published: February 21, 2013
© 2013 American Chemical Society
1500
dx.doi.org/10.1021/om400001e | Organometallics 2013, 32, 1500−1506

Organometallics
Article
(m), 1242 (m), 1158 (w), 1114 (m), 1082 (m), 1028 (w), 999 (w),
959 (m), 832 (s), 741 (s), 724 (s), 705 (s), 690 (s), 667 (s), 633 (s),
611 (s), 590 (s), 550 (m), 538 (m), 513 (s), 490 (s), 441 (m), 414
(m). Anal. Calcd for C30H34Cl2DyNO0.5P2SSi (2a·0.5THF) (772.11):
C, 46.67; H, 4.44; N, 1.81, S, 4.15. Found: C, 46.79; H, 4.08; N, 1.49;
S, 4.81.
lithium(iminophosphoranyl)(thiophosphoranyl)methanide [Li-
{CH(PPh2NSiMe3)(PPh2S)}]. Furthermore, the corre-
sponding dianion [Li2{(PPh2NSiMe3)(PPh2S)}] was
obtained by the reaction of [CH2(PPh2NSiMe3)(PPh2
S)] with tBuLi. Soon after, the derivatives of Mg,53 Al,53 and
Sn54,55 were also synthesized by the same group.
2b: ErCl3 (122 mg, 0.45 mmol). Yield: 120 mg, 0.15 mmol, 41%
pink crystals. IR (ATR): ν (cm−1) 3054 (w), 2953 (w), 2855 (w),
1588 (w), 1483 (w), 1437 (m), 1312 (w), 1255 (w), 1183 (w), 1111
(w), 1064 (w), 1092 (w), 994 (w), 898 (w), 845 (m), 786 (m), 773
(m), 738 (s), 687 (s), 633 (m), 604 (m), 529 (m), 500 (s), 480 (s).
Anal. Calcd for C28H30Cl2ErNP2SSi (2b·THF) (740.82): C, 45.40; H,
4.08; N, 1.89; S, 4.33. Found: C, 45.48; H, 3.87; N, 1.43; S, 4.29.
[{CH(PPh2NSiMe3)(PPh2S)}Ln{N(SiHMe2)2}2] (Ln = Y (3a),
Sm (3b), Er (3c), Lu (3d)). [Ln{N(SiHMe2)2}3(THF)2] (1 equiv)
and [CH2(PPh2NSiMe3)(PPh2S)] (1 equiv) were dissolved in
toluene (20 mL). The clear solution was heated at reflux for 48 h and
was then reduced to dryness, extracted with pentane, and filtered. The
filtrate was concentrated and cooled to −78 °C, and a white (Ln = Y,
Lu) to slightly yellow (Ln = Sm) or pink (Ln = Er) precipitate was
formed.
3a: 376 mg (0.60 mmol) of [Y{N(SiHMe2)2}3(THF)2] and 300 mg
(0.60 mmol) of [CH2(PPh2NSiMe3)(PPh2S)]. Yield: 457 mg,
0.53 mmol, 83%. 1H NMR (300.13 MHz, THF-d8): δ (ppm) −0.03 (s,
9 H, Si(CH3)3), 0.01 (br, m, 24 H, SiH(CH3)2), 2.14 (dd, 1 H, CH),
4.71 (s, br, 4 H, SiH(CH3)2), 6.91 (br, 2 H, PPh), 7.03−7.11 (m, br, 4
H PPh), 7.38 (br, 5 H, PPh), 7.56−7.69 (m, br, 5 H, PPh), 7.95−8.00
(m, br, 2 H, PPh), 8.13 (br, 2 H, PPh). 31P{1H} NMR (121.49 MHz,
THF-d8): δ (ppm) 20.3 (dd, PNSi(CH3)3, 2J(P,Y) = 6.6 Hz, 2J(P,P) =
9.2 Hz), 32.3 (dd, PS, 2J(P,Y) = 5.8 Hz, 2J(P,P) = 9.5 Hz). 31P{1H,89Y}
NMR (121.49 MHz, THF-d8): δ (ppm) 20.6 (d, PNSi(CH3)3, 2J(P,P)
= 8.7 Hz), 32.3 (dd, PS, 2J(P,P) = 8.8 Hz). 89Y NMR (20 MHz, THF-
d8): δ (ppm) 476.5 . IR (ATR): ν (cm−1) 3055 (w), 2950 (w), 2896
(w), 2111 (s), 1589 (w), 1483 (w), 1436 (s), 1300 (w), 1246 (s), 1157
(m), 1105 (m), 1066 (m), 998 (m), 895 (m), 862 (m), 827 (s), 768
(m), 741 (s), 726 (s), 706 (m), 688 (s), 649 (m), 632 (m), 613 (m),
591 (m), 551 (m), 500 (m), 482 (m). Anal. Calcd for
C36H58N3P2SSi5Y (856.21): C, 50.50; H, 6.83; N, 4.91; S, 3.74.
Found: C, 51.00; H, 6.61; N, 4.81; S, 3.78.
3b: 343 mg (0.50 mmol) of [Sm{N(SiHMe2)2}3(THF)2] and 250
mg (0.50 mmol) of [CH2(PPh2NSiMe3)(PPh2S)]. Yield: 422
mg, 0.46 mmol, 92%. 31P{1H} NMR (121.49 MHz, THF-d8): δ (ppm)
38.6 (s, br, PNSi(CH3)3, 45.9 (s, br, PS). IR (ATR): ν (cm−1) 3055
(w), 2950 (w), 2896 (w), 2050 (w), 1924 (w), 1576 (w), 1559 (w),
1540 (w), 1482 (w), 1436 (m), 1304 (w), 1243 (m), 1158 (w), 1113
(w), 1078 (w), 1052 (w), 1028 (w), 985 (m), 943 (m), 891 (s), 829
(s), 780 (m), 762 (s), 742 (m), 734 (m), 724 (m), 690 (s), 665 (m),
632 (m), 607 (m), 589 (m), 550 (m), 513 (m), 495 (m), 437 (m),
416 (m). Anal. Calcd for C36H58N3P2SSi5Sm (917.67): C, 47.12; H,
6.37; N, 4.58; S, 3.49. Found: C, 47.32; H, 6.22; N, 4.41; S, 3.49. Only
broad noncharacteristic signals are observed in the 1H NMR spectrum.
3c: 343 mg (0.50 mmol) of [Er{N(SiHMe2)2}3(THF)2] and 250
mg (0.50 mmol) of [CH2(PPh2NSiMe3)(PPh2S)]. Yield: 262
mg, 0.28 mmol, 56%. IR (ATR): ν (cm−1) 3055 (w), 2950 (w), 2851
(w), 2064 (w), 1919 (w), 1699 (w), 1685 (w), 1653 (w), 1577 (w),
1559 (w), 1541 (w), 1522 (w), 1507 (w), 1483 (w), 1437 (w), 1303
(w), 1243 (w), 1157 (w), 1112 (w), 1063 (m), 1027 (m), 997 (m),
938 (m), 892 (s), 829 (s), 782 (m), 764 (s), 742 (s), 726 (s), 689 (s),
667 (m), 632 (m), 613 (m), 591 (m), 550 (m), 512 (m), 495 (m),
482 (m), 438 (m), 419 (m). Anal. Calcd for C36H58ErN3P2SSi5
(934.56): C, 46.27; H, 6.26; N, 4.50; S, 3.43. Found: C, 46.30; H,
6.35; N, 4.27; S, 3.45.
Herein we report on the coordination chemistry of the
(iminophosphoranyl)(thiophosphoranyl)methanide ligand
{CH(PPh2NSiMe3)(Ph2PS)}− in rare-earth-element chem-
istry. First, the dimeric species [K{CH(PPh2NSiMe3)-
(PPh2S)}]2 is described, which proved to be a suitable
transfer reagent for the ligand. Then, we describe the
preparation of the lanthanide chloride derivatives [{CH-
(PPh2NSiMe3)(PPh2S)}LnCl2(THF)] (Ln = Dy, Er)
and the amido compounds [{CH(PPh2NSiMe3)(PPh2
S)}Ln{N(SiHMe2)2}2] (Ln = Y, Sm, Er, Lu).
EXPERIMENTAL SECTION
■
All manipulations of air-sensitive materials were performed with the
rigorous exclusion of oxygen and moisture in flame-dried Schlenk-type
glassware either on a dual-manifold Schlenk line, interfaced to a high-
vacuum (10−3 mbar) line, or in an argon-filled MBraun glovebox. THF
was distilled under nitrogen from potassium benzophenone ketyl prior
to use. Hydrocarbon solvents (toluene and n-pentane) were dried
using a MBraun solvent purification system (SPS-800). Tetrahy-
drofuran was distilled under nitrogen from K/benzophenone ketyl
prior to use. All solvents were stored in vacuo over LiAlH4 in
resealable flasks. Deuterated solvents were obtained from Aldrich
GmbH (99 atom % D) and were degassed, dried, and stored in vacuo
over Na/K alloy in resealable flasks. NMR spectra were recorded on a
Bruker Avance II 300 MHz or Avance 400 MHz NMR spectrometer.
Chemical shifts are referenced to internal solvent resonances and are
reported relative to tetramethylsilane (1H and 29Si NMR), 85%
phosphoric acid (31P NMR), and Y(NO3)3 in H2O (89Y NMR),
respectively. IR spectra were obtained on a Bruker Tensor 37
instrument. Elemental analyses were carried out with an Elementar
Vario EL or Micro cube instrument. [CH2(PPh2NSiMe3)(PPh2
S)],52 LnCl3 (Ln = Dy, Er),56 and [Ln{N(SiHMe2)2}(THF)2] (Ln =
Y, Sm, Er, Lu)57 were prepared according to literature procedures.
[K{CH(PPh2NSiMe3)(PPh2S)}]2 (1). A 25 mL portion of THF
was added to a mixture of 0.17 g (4.23 mmol) of KH and 1.25 g (2.49
mmol) of [CH2(PPh2NSiMe3)(PPh2S)], and the mixture was
refluxed overnight. The remaining KH was then filtered off and the
solvent evaporated in vacuo. The remaining solid was washed with n-
pentane and dried in vacuo. Finally, the product was crystallized from
1
hot toluene. Yield: 1.20 g, 1.10 mmol, 89%. H NMR (300.13 MHz,
THF-d8): δ (ppm) −0.22 (s, 9 H, Si(CH3)3), 2.23 (d, 1H, CH, J(H,P
= 13.9 Hz), 7.05 (s, 12 H, Ph), 7.76 (m, 4 H, Ph), 8.13 (m, 4 H, Ph).
29Si{1H}NMR (49.7 MHz, THF-d8): δ (ppm) −15.7. 31P{1H} NMR
(121.49 MHz, THF-d8): δ (ppm) 9.1 (d, PNSi(CH3)3, 2J(P,P) = 18.0
2
Hz), 33.3. (d, PS, J(P,P) = 18.0 Hz). IR (ATR): ν (cm−1) 3071 (w),
3054 (w), 2946 (w), 1475 (w), 1434 (s), 1305 (w), 1247 (w), 1236
(w), 1188 (w), 1169 (s), 1098 (m), 1071 (w), 1027 (w), 1002 (w),
965 (m), 863 (m), 825 (s), 801 (m), 741 (s), 693 (vs), 667 (m), 620
(w), 591 (m), 573 (vs), 527 (s), 496 (s), 472 (m), 446 (s). Anal. Calcd
for C28H30KNP2SSi (541.74): C, 62.08; H, 5.58; N, 2.59; S, 5.92.
Found: C, 62.29; H, 5.76; N, 2.53; S, 5.86.
[{CH(PPh2NSiMe3)(PPh2S)}LnCl2(THF)] (Ln = Dy (2a), Er
(2b)). A 25 mL portion of THF was condensed at −196 °C onto a
mixture of 0.45 mmol of LnCl3 (Ln = Dy, Er) and 200 mg (0.18
mmol) of [K{CH(PPh2NSiMe3)(PPh2S)}]2, and the mixture was
stirred overnight at room temperature. The solution was then filtered
and the solvent removed in vacuo. The remaining solid was washed
with pentane and dried in vacuo. Finally, the product was crystallized
from THF/pentane.
3d: 355 mg (0.50 mmol) of [Lu{N(SiHMe2)2}3(THF)2] and 250
mg (0.50 mmol) of [CH2(PPh2NSiMe3)(PPh2S)]. Yield: 367
1
mg, 0.39 mmol, 78%. H NMR (300.13 MHz, THF-d8): δ (ppm)
−0.31 (br, 12 H, SiH(CH3)2), 0.12 (s, 9 H, Si(CH3)3), 0.28 (br, 12 H,
SiH(CH3)2), 2.18 (dd, 1 H, CH), 4.46 (s, br, 2 H, SiH(CH3)2), 5.01
(s, br, 2 H, SiH(CH3)2), 6.89 (br, 2 H, PPh), 7.01−7.16 (m, br, 4 H
PPh), 7.37 (br, 5 H, PPh), 7.54−7.76 (m, br, 5 H, PPh), 7.92−7.98
(m, br, 2 H, PPh), 8.10 (br, 2 H, PPh). 31P{1H} NMR (121.49 MHz,
2a: DyCl3 (121 mg, 0.45 mmol). Yield: 129 mg, 0.16 mmol, 43%
colorless crystals. IR (ATR): ν (cm−1) 3054 (w), 2923 (m), 2853 (w),
1685 (w), 1541 (w), 1522 (w), 1457 (w), 1436 (m), 1305 (w), 1255
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Article
Scheme 1. Synthesis of the Dimeric Compound [K{CH(PPh2NSiMe3)(PPh2S)}]2 (1)
2
THF-d8): δ (ppm) 21.3 (d, PNSi(CH3)3, J(P,P) = 9.5 Hz), 31.4 (d,
PS, 2J(P,P) = 9.5 Hz). IR (ATR): ν (cm−1) 3055 (w), 2951 (w), 2896
(w), 2075 (w), 1483 (w), 1437 (w), 1303 (w), 1243 (m), 1157 (w),
1111 (w), 1061 (w), 1027 (w), 998 (w), 980 (w), 936 (w), 891 (s),
829 (s), 783 (m), 764 (s), 742 (m), 726 (s), 703 (m), 689 (s), 668
(m), 632 (w), 615 (m), 592 (m), 550 (w), 513 (m), 497 (m), 483
(m). Anal. Calcd for C36H58LuN3P2SSi5 (942.27): C, 45.89; H, 6.20;
N, 4.46; S, 3.40. Found: C, 46.37; H, 6.09; N, 4.40; S, 3.25.
Alternative Route to 3c. [{CH(PPh2NSiMe3)(PPh2S)}-
LnCl2(THF)] (Ln = Er) (200 mg, 0.25 mmol) and KN(SiHMe2)2
(86 mg, 0.50 mmol) were dissolved in THF and refluxed overnight.
The solution was then reduced to dryness, extracted with pentane, and
filtered. The filtrate was dried in vacuo. Finally, the product was
crystallized from hot heptane. Yield: 140 mg, 0.15 mmol, 60% pink
crystals. The identity of the substance was determined by measuring
the lattice constants.
= 9189.1(6) Å3, T = 150(2) K, space group P21, Z = 8, μ(Mo Kα) =
1.542 mm−1, 61128 reflections measured, 32935 independent
reflections (Rint = 0.0956). The final R1 value was 0.0548 (I >
2σ(I)). The final wR2(F2) value was 0.0865 (all data). The goodness
of fit on F2 was 0.803. Flack parameter = 0.289(10).
Crystal data for 3b: C36H58N3P2SSi5Sm, M = 917.65, monoclinic, a
= 18.1063(5) Å, b = 18.3094(8) Å, c = 28.5034(9) Å, β = 92.609(2)°,
V = 9439.5(6) Å3, T = 150(2) K, space group P21/c, Z = 8, μ(Mo Kα)
= 1.509 mm−1, 61271 reflections measured, 17150 independent
reflections (Rint = 0.0963). The final R1 value was 0.0760 (I > 2σ(I)).
The final wR2(F2) value was 0.1355 (all data). The goodness of fit on
F2 was 0.991.
Crystal data for 3c: C36H58ErN3P2SSi5, M = 934.56, monoclinic, a
= 17.9443(6) Å, b = 18.0724(3) Å, c = 28.2270(10) Å, β = 92.458(3)°,
V = 9145.5(5) Å3, T = 150(2) K, space group P21, Z = 8, μ(Mo Kα) =
2.109 mm−1, 126151 reflections measured, 31781 independent
reflections (Rint = 0.0763). The final R1 value was 0.0293 (I >
2σ(I)). The final wR2(F2) value was 0.0583 (all data). The goodness
of fit on F2 was 0.820. Flack parameter = 0.308(9).
Crystal data for 3d: C36H58LuN3P2SSi5, M = 942.27, monoclinic, a
= 18.0044(4) Å, b = 18.1553(4) Å, c = 28.2986(6) Å, β = 92.596(2)°,
V = 9240.6(3) Å3, T = 150(2) K, space group P21/c, Z = 8, μ(Mo Kα)
= 2.408 mm−1, 189329 reflections measured, 17285 independent
reflections (Rint = 0.0663). The final R1 value was 0.0679 (I > 2σ(I)).
The final wR2(F2) value was 0.1152 (all data). The goodness of fit on
F2 was 1.284.
X-ray Crystallographic Studies of 1, 2a,b and 3a−d. A suitable
crystal was covered in mineral oil (Aldrich) and mounted on a glass
fiber. The crystal was transferred directly to a −73 °C or −123 °C cold
stream of a STOE IPDS 2 diffractometer.
All structures were solved by direct methods (SHELXS-97).58 The
remaining non-hydrogen atoms were located from successive differ-
ence in Fourier map calculations. The refinements were carried out by
using full-matrix least-squares techniques on F, minimizing the
2
2
function (Fo − Fc)2, where the weight is defined as 4Fo /2(Fo ) and
Fo and Fc are the observed and calculated structure factor amplitudes,
respectively, using the program SHELXL-97.58 Carbon-bound hydro-
gen atom positions were calculated. The final values of refinement
parameters are given in the Supporting Information. The locations of
the largest peaks in the final difference Fourier map calculation as well
as the magnitude of the residual electron densities in each case were of
no chemical significance. Positional parameters, hydrogen atom
parameters, thermal parameters, and bond distances and angles have
been deposited as Supporting Information.
RESULTS AND DISCUSSION
■
So and co-workers recently reported on the lithium
(iminophosphoranyl)(thiophosphoranyl)methanide compound
[Li{CH(PPh2NSiMe3)(PPh2S)}], which was obtained by
deprotonation of {CH2(PPh2NSiMe3)(PPh2S)}with
nBuLi.52 Previously we had experienced the difficulty of
isolation of the products from the LiCl byproduct formed by
a salt metathesis of LnCl3 with lithium reagents. LiCl tends to
be incorporated into rare-earth-metal compounds by forming
ate complexes.47 Therefore, we synthesized [K{CH(PPh2
NSiMe3)(PPh2S)}]2 (1) by treatment of {CH2(PPh2
NSiMe3)(PPh2S)} with KH in THF at 60 °C (Scheme 1).
Yellow single crystals are obtained by recrystallization from hot
toluene.
Crystal data for 1: C56H60K2N2P4S2Si2, M = 1083.44, monoclinic, a
= 11.5785(5) Å, b = 14.3272(5) Å, c = 16.7733(8) Å, β = 97.621(4)°,
V = 2757.9(2) Å3, T = 150(2) K, space group P21/n, Z = 2, μ(Mo Kα)
= 0.446 mm−1, 17297 reflections measured, 4994 independent
reflections (Rint = 0.0769). The final R1 value was 0.0403 (I >
2σ(I)). The final wR2(F2) value was 0.0570 (all data). The goodness
of fit on F2 was 0.803.
Crystal data for 2a: C32H38Cl2DyNOP2SSi, M = 808.12,
monoclinic, a = 9.7784(2) Å, b = 33.7778(11) Å, c = 11.5709(3) Å,
β = 111.613(2)°, V = 3553.07(17) Å3, T = 200(2) K, space group P21/
c, Z = 4, μ(Mo Kα) = 2.461 mm−1, 20068 reflections measured, 6610
independent reflections (Rint = 0.0425). The final R1 value was 0.0291
(I > 2σ(I)). The final wR(F2) values were 0.0709 (all data). The
goodness of fit on F2 was 1.042.
Crystal data for 2b: C32H38Cl2ErNOP2SSi, M = 812.88,
monoclinic, a = 9.7471(2) Å, b = 33.7383(8) Å, c = 11.5597(2) Å,
β = 111.5964(14)°, V = 3534.55(12) Å3, T = 200(2) K, space group
P21/c, Z = 4, μ(Mo Kα) = 2.734 mm−1, 56385 reflections measured,
6597 independent reflections (Rint = 0.0609). The final R1 value was
0.0279 (I > 2σ(I)). The final wR2(F2) value was 0.0562 (all data). The
goodness of fit on F2 was 0.990.
Compound 1 was characterized by standard analytical and
spectroscopic techniques, and the solid-state structure was
determined by single-crystal X-ray diffraction analyses. The 1H,
29Si{1H}, and 31P{1H} NMR spectra show the expected sets of
signals. The 1H NMR spectrum reveals the characteristic signals
for the trimethylsilyl groups at δ −0.22 ppm and the methine
proton at δ 2.23 ppm. In [Li{CH(PPh2NSiMe3)(PPh2
S)}], the latter signal is split into a doublet and the expected
coupling with the two nonequivalent phosphorus atoms is not
observed.52 In the 31P{1H} NMR, two characteristic signals for
the two nonequivalent phosphorus atoms are seen at δ 9.1 and
33.3 ppm as doublets with a coupling constant of 18.0 Hz. In
Crystal data for 3a: C36H58N3P2SSi5Y, M = 856.21, monoclinic, a =
17.9574(8) Å, b = 18.1055(5) Å, c = 28.2892(10) Å, β = 92.465(3)°, V
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comparison to {CH2(PPh2NSiMe3)(PPh2S)} (δ(31P-
{1H}) −5.23 and 36.7 ppm) no uniform shifting of the signals
can be observed. In the IR spectrum of compound 1 strong
bands are observed for the PN (ν 1236 cm−1)59 and the P
S (ν 693 cm−1)60 stretching vibrations.
Compound 1 crystallizes in the monoclinic space group P21/
n, having four molecules in the unit cell. Compound 1 forms a
dimeric structure in the solid state, having a central K−S−K′−
S′ plane (Figure 1). Two potassium atoms are bridged by the
K{CH(PPh2NSiMe3)(PPh2S)} moiety to the potassium
atom is observed. In this discussion we consider all C−K
interactions up to a value of 3.6 Å as bonds, which is a
conservative limit for K−C interactions.62−64 The K−C
distances range from 3.247(3) to 3.390(3) Å of the η6-bound
phenyl ring, indicating an almost symmetrical coordination.
The K−ring centroid distance is 2.969(1) Å. Moreover, the
potassium atoms have a short contact to one of the methyl
groups of the SiMe3 unit (K−C26 = 3.127 Å) which may be
considered as a γ-agostic interaction.
The reaction of 1 with the anhydrous lanthanide trichlorides
LnCl3 (Ln = Dy, Er) at room temperature after workup
resulted in the monomeric compounds [{CH(PPh2
NSiMe3)(PPh2S)}LnCl2(THF)] (Ln = Dy (2a), Er (2b))
in moderate yields as single-crystal materials (Scheme 2). Both
compounds were characterized by IR and elemental analysis,
and the structure of each compound was established by single-
crystal X-ray diffraction. In the IR spectra the expected
characteristic bands for the PN (ν 1242 cm−1 (2a) and
1243 cm−1 (2b))59 and the PS stretching vibrations (ν 690
60
−1
cm−1 (2a) and ν 689 cm (2b)) are observed.
Compounds 2a,b, which are isostructural with each other,
both crystallize in the monoclinic space group P21/n with one
molecule in the asymmetric unit (Figure 2). In contrast to the
corresponding bis(phosphinimino)methanide complexes
35
[{CH(PPh2NSiMe3)2}LnCl2]2 compounds 2a,b are not
Figure 1. Perspective ORTEP view of the molecular structure of 1.
Thermal ellipsoids are drawn to encompass 50% probability.
Hydrogen atoms are omitted for clarity. Selected distances (Å) and
angles (deg): K−N = 2.817(2), K−S = 3.1452(10), K−S′ =
3.1948(10), K−C1 4.262 Å, K−C26 = 3.127, K−Cg = 2.9690(1),
S−P1 = 2.0110(10), N−P2 = 1.572(2); N−K−S = 85.59(5), N−K−S′
= 83.33(5), S−K−S′ = 102.98(3), N−K−Cg = 179.758(3), S−K−Cg′
= 85.83, S′−K−Cg′ = 94.16 (Cg = ring centroid).
bridged via the chloro atoms, resulting in monomeric species.
The remaining coordination site is filled by an additional
coordinating THF molecule. As observed in 1, the {CH-
(PPh2NSiMe3)(PPh2S)}− ligand coordinates with the
nitrogen and the sulfur atoms to the lanthanide atom, forming
a six-membered metallacycle (Ln−S−P1−C1−P2−N). How-
ever, in contrast to 1, a twist-boat conformation of the
metallacycle with a long interaction between the methanide
carbon atom (C1) and the lanthanide atom is observed. This
kind of conformation is typical for most of the known
bis(phosphinimino)methanide complexes of the early transition
metals and the lanthanides.1,34 When the Ln−C1 interaction
(Dy−C1 = 2.666(3) Å and Er−C1 = 2.629(3) Å) is considered
as a chemical bond, the lanthanide atoms are 6-fold
coordinated, forming a distorted-octahedral coordination
polyhedron. The other bond distances between the lanthanide
atoms and the coordinated atoms are in the expected range.
Thus, the Ln−N distances of 2.335(2) Å (2a) and 2.313(2) Å
(2b) are similar to those in [{CH(PPh2NSiMe3)2}DyCl2]2
(2.330(3) and 2.344(3) Å)35 and [{CH(PPh2NSiMe3)2}-
ErCl2]2 (2.327(6) and 2.344(6) Å).35 In comparison to the
soft sulfur atoms and not by the hard nitrogen atoms due to a
greater steric repulsion of the SiMe3 group which is bound to
the nitrogen atom. A crystallographic inversion center is
observed in the center of this plane. The monoanionic
{CH(PPh2NSiMe3)(PPh2S)}− ligand coordinates to the
potassium ion via the nitrogen and the sulfur atom, forming a
six-membered metallacycle (K−S−P1−C13−P2−N). In con-
trast to the corresponding bis(phosphinimino)methanide
compound [K{CH(PPh2NSiMe3)2}] no interaction was
observed between the methanide carbon atom (C1) and K.61
The K−C1 distance is 4.262 Å. Due to the dimerization, a η6
coordination of one phenyl ring of the symmetry-equivalent
Scheme 2. Synthesis of [{CH(PPh2NSiMe3)(PPh2S)}LnCl2(THF)] (Ln = Dy (2a), Er (2b))
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NSiMe3)(PPh2S)} with [Ln{N(SiHMe2)2}3(THF)2] (Ln =
Y, Sm, Er, Lu) (Anwander amides)57 in refluxing toluene
resulted in the bis(amido) complexes [{CH(PPh2NSiMe3)-
(PPh2S)}Ln{N(SiHMe2)2}2] (Ln = Y (3a), Sm (3b), Er
(3c), Lu (3d)) in high yields (Scheme 3). The new complexes
have been characterized by standard analytical and spectro-
scopic techniques, and the solid-state structures of all four
compounds were established by single-crystal X-ray diffraction.
Next, we investigated an alternative synthetic approach to the
amido complexes 3a−d. Reaction of the chloro complex 2b
with 2 equiv of KN(SiHMe2)2 in refluxing THF resulted in the
amido complex 3c in 60% yield (Scheme 4). Since the yield was
lower by using this salt metathesis, we did not further explore
this approach.
The diamagnetic yttrium and lutetium compounds 3a,d and
the samarium compound 3b were investigated by NMR
1
spectroscopy. For 3a H, 31P{1H}, 31P{1H,89Y}, and 89Y NMR
1
spectra were recorded. In the H NMR spectra of 3a,d the
signals are broadened due to certain dynamic behavior. The
characteristic signals for the methine proton are observed at δ
2.14 (3a) and 2.18 ppm (3d). In comparison to 1 this signal is
shifted slightly upfield and the expected coupling pattern is
clearly seen. Other characteristic signals are the singlets of the
SiMe3 group of the ligand and the SiMe2 group of the amide.
Moreover, a broad signal can be observed for the protons of the
SiH group at δ 4.71 (3a) and 4.46 ppm (3d). In the 31P{1H}
NMR spectrum of 3a two doublets of doublets are seen at δ
Figure 2. Perspective ORTEP view of the molecular structure of 2a.
Thermal ellipsoids are drawn to encompass 50% probability.
Hydrogen atoms are omitted for clarity. Selected distances (Å) and
angles (deg) are as follows (data for the isostructural compound 2b are
also given). 2a: Dy−N = 2.335(2), Dy−S = 2.8469(8), Dy−O =
2.351(2), Dy−Cl1 = 2.5594(8), Dy−Cl2 = 2.5457(9), Dy−C1 =
2.666(3), S−P1 = 2.0076(11), N−P2 = 1.604(2), P1−C1 = 1.747(3),
P2−C1 = 1.754(3); N−Dy−O = 161.78(8), N−Dy−Cl1 = 100.44(6),
N−Dy−Cl2 = 93.03(6), N−Dy−S = 91.01(6), N−Dy C1 = 65.08(8),
O−Dy−Cl1 = 97.61(6), O−Dy−Cl2 = 84.97(6), O−Dy−C1 =
97.20(9), Cl1−Dy−Cl2 = 104.08(4), Cl1−Dy−S = 92.48(3), Cl1−
Dy−C1 = 154.39(7), Cl2−Dy−S = 161.92(3), Cl2−Dy−C1 =
97.93(7), S−Dy−O = 85.70(6), S−Dy−C1 = 67.95(6), C1−P1−C2
= 106.10(14). 2b: Er−N = 2.313(2), Er−S = 2.8224(9), Er−O =
2.332(2), Er−Cl1 = 2.5318(9), Er−Cl2 = 2.5215(10), Er−C1 =
2.629(3), S−P1 = 2.0057(12), N−P2 = 1.598(3), P1−C1 = 1.748(3),
P2−C1 = 1.755(3); N−Er−O = 162.16(10), N−Er−Cl1 = 100.29(7),
N−Er−Cl2 = 93.07(7), N−Er−S = 91.38(7), N−Er−C1 = 65.67(9),
O−Er−Cl1 = 97.36(7), O−Er−Cl2 = 85.27(7), O−Er−S = 85.29(7),
O−Er−C1 = 96.91(10), Cl1−Er−Cl2 = 103.68(4), Cl1−Er−S =
92.24(3), Cl1−Er−C1 = 154.97(7), Cl2−Er−S = 162.40(3), Cl2−Er−
C1 = 97.90(7), S−Er−C1 = 68.58(7), P1−C1−P2 = 124.0(2).
2
20.3 and 32.3 ppm which are the result of a J(P,P) and a
2J(P,Y) coupling. For 3d two doublets are seen in the 31P{1H}
NMR at δ 21.3 and 31.4 ppm. In the 89Y NMR spectrum of 3a
the P,Y coupling could not be properly resolved and a broad
peak is seen at δ 476.5 ppm. For the samarium complex 3b only
1
broad and noncharacteristic signals are observed in the H
NMR spectrum. In the 31P{1H} NMR spectrum the expected
two signals are seen at δ 38.6 and 45.9 ppm. Due to the
paramagnetic metal center the observed chemical shifts are
significantly different in comparison to compounds 3a,d.
Single crystals of compounds 3a−d were obtained from
toluene. Although the quality of all crystals was poor, the
structures of compounds 3a−d could be fully refined (Figure
3). The structures of compounds 3b,d were refined in the
monoclinic space group P21/c with two molecules in the
asymmetric unit. The structures of compounds 3a,c were
refined in the monoclinic space group P21 with four molecules
in the asymmetric unit. Compounds 3a,c both crystallize as
twins. As observed for 2a,b the {CH(PPh2NSiMe3)(PPh2
S)}− ligand coordinates with the nitrogen and the sulfur atoms
to the metal atom, forming a six-membered metallacycle (Ln−
S−P1−C1−P2−N). The Ln−S and Ln−N bond distances are
in the expected range. Moreover, a long bond between the
methanide carbon atom and the rare-earth ion is observed
neutral compound {CH2(PPh2NSiMe3)(PPh2S)}52 the
P−C bond distances of the {CH(PPh2NSiMe3)(PPh2S)}−
ligand in 2a,b are significantly shorter (P1−C1 = 1.747(3) Å,
P2−C1 = 1.754(3) Å (2a) and P1−C1 = 1.748(3) Å, P2−C1 =
1.755(3) Å (2b) vs 1.820(3) Å, 1.831(3) Å in {CH2(PPh2
NSiMe3)(PPh2S)}), indicating a certain level of delocaliza-
tion.
An alternative route of accessing (iminophosphoranyl)-
(thiophosphoranyl)methanide complexes of yttrium and the
lanthanides is amine elimination.65 Reaction of {CH2(PPh2
Scheme 3. Synthesis of [{CH(PPh2NSiMe3)(PPh2S)}Ln{N(SiHMe2)2}2] (Ln = Y (3a), Sm (3b), Er (3c), Lu (3d))
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Scheme 4. Alternative Synthetic Route to [{CH(PPh2NSiMe3)(PPh2S)}Er{N(SiHMe2)2}2] (3c)
hydrosilylation reactions41,42 we performed catalytic studies by
using compounds 3a,b as precatalysts for hydroamination/
cyclization reactions. Three different aminoolefins and one
aminoalkyne were used as substrates. All experiments were
carried out under rigorously anaerobic reaction conditions by
using dry, degassed substrates with 5 mol % catalyst loading.
Unfortunately, we could not obtain reproducible yields and
rates under the same reaction conditions. We suggest that
compounds 3a,b decompose under the reaction conditions.
SUMMARY
■
In summary, we have introduced the (iminophosphoranyl)-
(thiophosphoranyl)methanide {CH(PPh2NSiMe3)(PPh2
S)}− as a ligand into the chemistry of yttrium and the
lanthanides. First, the potassium reagent [K{CH(PPh2
NSiMe3)(PPh2S)}]2 was synthesized by deprotonation of
[CH2(PPh2NSiMe3)(PPh2S)] with KH. [K{CH(PPh2
NSiMe3)(PPh2S)}]2 is dimeric in the solid state. The rare-
earth-metal complexes of the ligand were obtained either by salt
metathesis from [K{CH(PPh2NSiMe3)(PPh2S)}]2 and
LnCl3 or by an amine elimination from the amides [Ln{N-
(SiHMe2)2}3(THF)2] and the neutral ligand {CH2(PPh2
NSiMe3)(PPh2S)}. Salt metathesis led to the dichloro
complexes [{CH(PPh2NSiMe3)(PPh2S)}LnCl2(THF)]
(Ln = Dy, Er). The bis(amido) compounds [{CH(PPh2
NSiMe3)(PPh2S)}Ln{N(SiHMe2)2}2] were obtained by
amine elimination. The amido complex [{CH(PPh2
NSiMe3)(PPh2S)}Er{N(SiHMe2)2}2] could also be accessed
by a reaction of [{CH(PPh2NSiMe3)(PPh2S)}-
ErCl2(THF)] with KN(SiHMe2)2.
Figure 3. Perspective ORTEP view of the molecular structure of 3d.
Shown is one of two independent molecules in the asymmetric unit.
Thermal ellipsoids are drawn to encompass 50% probability.
Hydrogen atoms are omitted for clarity. Selected distances (Å) and
angles (deg) (data for the analogous compounds 3a−c are given in the
Supporting Informations): Lu1−N1 = 2.298(5), Lu1−N2 = 2.193(7),
Lu1−N3 = 2.197(6), Lu1−S1 = 2.808(2), Lu1−C1 = 2.654(7), S1−
P1 = 1.995(3), N1−P2 = 1.605(6), P1−C1 = 1.736(7), P2−C1 =
1.749(7), Lu2−N4 = 2.292(6), Lu2−N5 = 2.182(6), Lu2−N6 =
2.165(6), Lu2−C37 = 2.702(6), Lu2−S2 = 2.739(2), S2−P3 =
2.019(3), N4−P4 = 1.602(6), P3−C37 = 1.736(8), P4−C37 =
1.741(7); N1−Lu1−N2 = 117.3(3), N1−Lu1−N3 = 111.2(2), N1−
Lu1−S1 = 96.75(15), N1−Lu1−C1 = 66.4(2), N2−Lu1−N3 =
106.0(3), N2−Lu1−S1 = 89.0(2), N2−Lu1−C1 = 156.8(2), N3−
Lu1−S1 = 136.1(2), N3−Lu1−C1 = 92.5(2), S1−Lu1−C1 =
67.87(15), P1−C1−P2 = 124.5(4), N4−Lu2−N5 = 112.6(3), N4−
Lu2−N6 = 122.0(3), N4−Lu2−S2 = 98.2(2), N4−Lu2−C37 =
65.4(2), N5−Lu2−N6 = 104.7(3), N5−Lu2−S2 = 89.9(2), N5−Lu2−
C37 = 157.6(2), N6−Lu2−S2 = 125.2(2), N6−Lu2−C37 = 94.0(2),
S2−Lu2−C37 = 68.9(2), P3−C37−P4 = 126.9(4).
ASSOCIATED CONTENT
* Supporting Information
■
S
CIF files giving X-ray crystallographic data for the structure
determinations of 1, 2a,b, and 3a−d. This material is available
free of charge via the Internet at http://pubs.acs.org.
(average 2.712 (3a), 2.808 (3b), 2.697 (3c), 2.678 Å (3d)).
Within the ligand scaffold the P−Cmethanide bonds are
significantly shorter than in the neutral compound
{CH2(PPh2NSiMe3)(PPh2S)}. In addition to the {CH-
AUTHOR INFORMATION
Corresponding Author
*roesky@kit.edu.
■
(PPh2NSiMe3)(PPh2S)}− ligand, two N(SiHMe2)2
−
groups coordinate to the metal center as well. The Ln−N
bond distances of the N(SiHMe2)2 groups are about 0.1 Å
Present Address
−
†Division of Chemistry, Graduate School of Engineering
Science, Osaka University, Japan.
shorter than the Ln−N distance of the {CH(PPh2NSiMe3)-
(PPh2S)}− ligand. When the {CH(PPh2NSiMe3)(PPh2
S)}− ligands are considered as tridentate, the metal centers are
5-fold coordinated, resulting in a distorted-trigonal-bipyramidal
coordination polyhedron with the methanide carbon atom and
Notes
The authors declare no competing financial interest.
−
ACKNOWLEDGMENTS
one N(SiHMe2)2 group in the two apical positions.
■
Since the corresponding bis(phosphinimino)methanide bis-
(amido) complexes [{CH(PPh2NSiMe3)2}Ln{N-
(SiHMe2)2}2] were used successfully in hydroamination/
cyclization, hydrosilylation, and sequential hydroamination/
This work was supported by the Alexander-von-Humboldt
Stiftung (Fellowship for B.M.), the Helmholtz Research School:
Energy-Related Catalysis, and the DFG-funded transregional
collaborative research center SFB/TRR 88 “3MET”.
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