The reactivity of (CH3C5H4)2LnNPh2(THF) (Ln = Y, Yb) with CS2 and PhNCS: Synthesis and crystal structures

Article abstract of DOI:10.1021/om0109509

The insertion reactions of CS₂ and phenyl isothiocyanate into the Ln-N bond of lanthanocene diphenylamide were first studied, and the insertion products, viz., [(CH₃C₅H₄)₂-Y(η²-S ₂CNPh₂)]₂·CH₃C₆H ₅ (1), [(CH₃C₅H₄)₂Yb(η²-S ₂CNPh₂)] (2), and {(CH₃C₅H₄)₂Y[η²-SC(NP h₂)NPh]} (3), were obtained. All the new complexes were characterized by single-crystal X-ray diffraction. Both 1 and 3 have dimeric structure, which have an interlinked tricycle formed via two bridged S atoms, while 2 exists as a monomer.

Full text of DOI:10.1021/om0109509

Organometallics 2002, 21, 2529-2532
2529
Notes
Th e Rea ctivity of (CH3C5H4)2Ln NP h 2(THF ) (Ln ) Y, Yb)
w ith CS2 a n d P h NCS: Syn th esis a n d Cr ysta l Str u ctu r es
Huanrong Li,† Yingming Yao,† Qi Shen,*,†,‡ and Linhong Weng§
Department of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215006,
People’s Republic of China, State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People’s
Republic of China, and Department of Chemistry, Fudan University,
Shanghai 200433, People’s Republic of China
Received November 2, 2001
Summary: The insertion reactions of CS2 and phenyl
isothiocyanate into the Ln-N bond of lanthanocene
diphenylamide were first studied, and the insertion
products, viz., [(CH3C5H4)2Y(η2-S2CNPh2)]2‚CH3C6H5
(1), [(CH3C5H4)2Yb(η2-S2CNPh2)] (2), and {(CH3C5H4)2Y-
[η2-SC(NPh2)NPh]} (3), were obtained. All the new
complexes were characterized by single-crystal X-ray
diffraction. Both 1 and 3 have dimeric structure, which
have an interlinked tricycle formed via two bridged S
atoms, while 2 exists as a monomer.
For some time now, we have engaged in studies on
the reactivity of organolanthanide amide with small
molecules.7-9 As part of our studies, we have recently
found that lanthanocene diphenylamide, (CH3C5H4)2-
LnNPh2(THF) (Ln ) Y, Yb), is also able to react with
CS2 to give the corresponding dithiocarbaminate,
[(CH3C5H4)2Y(η2-S2CNPh2)]2‚CH3C6H5 (1) and [(CH3-
C5H4)2Yb(η2-S2CNPh2)] (2). In addition, the reaction of
(CH3C5H4)2YNPh2(THF) with PhNCS was also exam-
ined, as PhNCS is an isoelectronic analogue of CS2. The
reaction gives an insertion product, {(CH3C5H4)2Y[η2-
SC(NPh2)NPh]} (3), in good yield. Here we report the
results.
In tr od u ction
The insertion reactions of CS2 into the M-X bonds of
various main-group-metal or transition-metal complexes
have been studied extensively, and a variety of products,
such as coordinated dithioesters, dithiocarbaminates, or
similar types of compounds, can be obtained, depending
on the nature of M-X.1 For example, the complexes [Fe-
(η5-C5H5)(CtCR)(PPh3)] (R ) Ph, tBu), Cp*W(NO)-
(OCMe3)(NHCMe3), and Re(OCH3)(CO)3(PMe3)2 react
with CS2 to form the corresponding insertion products
[Fe(η5-C5H5)(S2CCtCR)(PPh3)],2 Cp*W(NO)(η2-S2CNH-
CCMe3)(OCMe3),3 and Re(η2-S2COCH3)(CO)3(PMe3)2,4
respectively.
However, the reactivity of organolanthanide com-
pounds with CS2 has still remained poorly explored. Up
to date, it is known only that organolanthanide com-
pounds containing a Ln-C bond, Cp2*Sm(η3-CH2-
CHCHCH3) and Cp2*YCH2Ph, can react with CS2 to
afford the corresponding dithioesters Cp2*Sm(η2-S2-
CCH2CHCHCH3)5 and Cp2*Y(η2-S2CH2Ph).6
Exp er im en ta l Section
All manipulations were performed under a pure argon
atmosphere using standard Schlenk techniques. Solvents were
refluxed and distilled from sodium/benzophenone ketyl prior
to use. CS2 and PhNCS were dried over 3 Å molecular sieves
for a week before distillation. (CH3C5H4)2LnNPh2(THF) (Ln
) Y, Yb) was prepared according to a literature method.9
Melting points were determined in a sealed argon-filled
capillary and are uncorrected. Lanthanide metal analyses were
carried out by complexometric titration. Carbon, hydrogen, and
nitrogen analyses were performed on a Carlo Erba 1110
spectrometer by direct combustion. The 1H and 13C NMR
spectra were recorded on an INOVA-400 instrument using
benzene-d6 as solvent. The IR spectra were recorded on a
Magna-550 spectrometer as KBr pellets.
P r ep a r a tion of [(CH3C5H4)2Y(η2-S2CNP h 2)]2‚CH3C6H5
(1). To a solution of (CH3C5H4)2YNPh2(THF) (20 mL, 5.4 mmol)
in toluene was added CS2 in excess (5 mL) at room tempera-
ture. The color of the solution immediately changed from
yellowish to dark red. The reaction mixture was stirred for 5
min and then concentrated to about 10 mL under reduced
pressure. Red crystals of 1 suitable for X-ray single-crystal
structure determination were obtained at -10 °C for 2 days.
Yield: 2.57 g (88.5%). Mp: 146-149 °C (dec). Anal. Calcd for
* To whom correspondence should be addressed. E-mail: qshen@
suda.edu.cn. Fax: 0086-512-65112371.
† Suzhou University.
‡ Shanghai Institute of Organic Chemistry.
§ Fudan University.
(1) Butler, I. S.; Fenster, A. E. J . Organomet. Chem. 1974, 66, 161.
(2) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J . Orga-
nomet. Chem. 1996, 510, 207.
(3) Legzdins, P.; Rettig, S. J .; Ross, K. J . Organometallics 1994, 13,
569.
C
57H56N2S4Y2: C, 63.68; H, 5.25; N, 2.61; Y, 16.54. Found: C,
63.50; H, 5.19; N, 2.54; Y, 16.47. 1H NMR: δ 7.28-7.41 (m,
(4) Simpson, R. D.; Bergman, R. G. Angew. Chem., Int. Ed. Engl.
1992, 31, 220.
(5) Evans, W. J .; Seibel, C. A.; Ziller, J . W.; Doedens, R. J .
Organometallics 1998, 17, 2103.
(7) Mao, L. S.; Shen, Q. J . Polym. Sci., Part A Polym. Chem. 1998,
36, 1593.
(8) Mao, L. S.; Shen, Q.; Xue, M. Q.; Sun, J . Organometallics 1997,
16, 3711.
(6) Den Haan, K. H.; Luinstra, G. A.; Meetsma, A.; Teuben, J . H.
Organometallics 1987, 6, 1509.
(9) Wang, Y.; Shen, Q.; Xue, F.; Yu, K. J . Organomet. Chem. 2000,
598, 359.
10.1021/om0109509 CCC: $22.00 © 2002 American Chemical Society
Publication on Web 05/14/2002

2530 Organometallics, Vol. 21, No. 12, 2002
Ta ble 1. Cr ysta l Da ta a n d Str u ctu r e Refin em en t for Com p lexes 1, 2, a n d 3
Notes
1
2
3
formula
fw
T (K)
C
57H56N2S4Y2
C25H24NS2Yb
575.61
293(2)
C62H58N4S2Y2
1101.06
293(2)
1075.10
293(2)
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
triclinic
P1h
orthorhombic
Pnma
9.667(12)
11.462(15)
21.00(3)
90.00
90.00
90.00
2327(5)
2
monoclinic
P21/n
15.4885(17)
9.5787(11)
18.2814(19)
90.00
103.695(2)
90.00
2635.1(5)
4
13.104(2)
13.553(2)
16.893(3)
67.1655(3)
71.210(3)
73.545(4)
2574.1(8)
2
Z
F(000)
1108
1.387
2.444
1132
1.643
4.209
1136
1.388
2.314
D(calc) (Mg/m3)
µ (mm-1
)
diffractometer
radiation
BRUKER SMART 1000
Mo KR
BRUKER SMART 1000
Mo KR
BRUKER SMART 1000
Mo KR
θ range (deg)
cryst size (mm)
no.of reflns collected
no. of obsd (I >2σ(I))
no. of variables
RF, RwF
1.35-26.40
0.45 × 0.35 × 0.30
10 303
6308
586
2.02-25.01
0.40 × 0.35 × 0.25
7639
2147
152
1.55-26.38
0.45 × 0.10 × 0.05
12 712
5363
432
0.0531, 0.1430
0.982
0.0615, 0.1202
1.252
0.0346, 0.0628
0.930
goodness of fit
25H, Ph), 5.87-6.10 (m, 16H, CH3C5H4), 2.34 (s, 3H, CH3C6H5),
2.22 (s, 12H, CH3C5H4). 13C NMR: δ 209.43 (CS2), 145.90,
137.20, 129.97, 129.76, 128.44, 125.70, 122.46, 118.49 (Ph),
112.97, 110.68, 108.43 (CH3C5H4), 21.89 (CH3C6H5), 16.06
(CH3C5H4). IR (KBr pellet, cm-1): 3061 (m), 2924 (w), 1610
(s), 1589 (m), 1490 (s), 1334 (s), 1302 (s), 1265 (s), 1049 (s),
1031 (m), 886 (m), 780 (s), 753 (s), 669 (s), 651 (s), 617 (s).
P r ep a r a tion of [(CH 3C5H4)2Yb(η2-S2CNP h 2)] (2). To a
solution of (CH3C5H4)2YbNPh2(THF) (10 mL, 1.50 mmol) in
toluene was added an excess of CS2. After stirring at room
temperature for 5 min, the solution was concentrated to about
6 mL and allowed to crystallize at -10 °C. Red crystals were
isolated. Yield: 0.74 g (85.7%). Mp: 138-141 °C (dec). Anal.
Calcd for C25H24NS2Yb: C, 52.16; H, 4.20; N, 2.43; Yb, 30.05.
Found: C, 52.07; H, 4.12; N, 2.36; Y, 29.98. 1H NMR: δ 6.46-
7.21 (m, 10H, Ph), -11.93 (s, 6H, CH3C5H4), -41.92 (s, 4H,
CH3C5H4), -46.70(s, 4H, CH3C5H4). IR (KBr pellet, cm-1):
3057 (w), 1588 (m), 1489 (s), 1347 (s), 1303 (s), 1260 (s), 1157
(s), 1048 (s), 1027 (s), 881 (s), 751 (s), 698 (s).
performed on an IBM-compatible PC with the SHELX-97
package.10 In the final cycles, the non-hydrogen atoms were
refined anisotropically, while hydrogen atoms were placed in
idealized positions.
Resu lts a n d Discu ssion
Syn th eses a n d Molecu la r Str u ctu r es of [(CH 3-
C5H 4)2Y(η2-S2CNP h 2)]2‚CH 3C6H 5 (1) a n d (CH 3-
C5H4)2Yb(η2-S2CNP h 2) (2). Reaction of excess CS2 with
a solution of (CH3C5H4)2LnNPh2(THF) (Ln ) Y, Yb) in
toluene for 5 min at room temperature gave a red-
colored complex with the constitution of a 1:1 adduct of
(CH3C5H4)2LnNPh2 (Ln ) Y, Yb) and CS2 according to
their elemental analyses and spectral data. The IR
spectra of the two products display ν(CS) absorption
peaks at 1031 and 886 cm-1 for 1, which are comparable
to those of related trithiocarbonate complexes,13 and at
1157 and 1048 cm-1 for 2, which can be attributed to
the symmetric and asymmetric stretching frequencies
of the C-S bond in [S2CNPh2]- fragments, respectively.
These data are also comparable to those observed in the
related CS2 insertion products, such as Cp*W(NO)(η2-
S2CNHCCMe3)(OCMe3),3 Cp*W(NO)(η2-S2CPh)(Ph),14
and Me2Al(µ-i-Pr2N)2Mg[SC(CH3)S].15 These results
obviously indicate a new C-N bond is formed via the
insertion reaction of CS2 into the Ln-N bond of orga-
nolanthanide amide in these reactions and the new
ligand dithiocarbaminate group, [Ph2NCS2 ]-, is coor-
dinated to the central metal Y or Yb in an η2 manner
(eqs 1 and 2). Although the analogous dithiocarbaminate
P r ep a r a tion of {(CH3C5H4)2Y[η2-SC(NP h 2)NP h ]}2 (3).
To a solution of (CH3C5H4)2YNPh2(THF) (17 mL, 4.59 mmol)
in toluene was added 0.54 mL of phenyl isothiocyanate
(PhNCS) (4.59 mmol). After the reaction mixture was stirred
at room temperature overnight, the solution was concentrated
and cooled to -10 °C for crystallization. Colorless crystals of
complex 3 were obtained. Yield: 1.52 g (60.1%). Mp: 169-
172 °C (dec). Anal. Calcd for C62H58N4S2Y2: C, 67.63; H, 5.31;
N, 5.09; Y, 16.15. Found: C, 67.46; H, 5.25; N, 4.98; Y, 16.07.
1H NMR: δ 7.03-7.26 (m, 30H, Ph), 5.84-6.11 (m, 16H,
CH3C5H4), 2.20 (s, 12H, CH3C5H4). 13C NMR: δ 149.09, 135.07,
129.74, 128.73, 124.80, 123.05, 122.71, 119.67 (Ph), 113.11,
112.50, 110.27 (CH3C5H4), 16.75 (CH3C5H4). IR (KBr pellet,
cm-1): 3062 (w), 1709 (s), 1592 (m), 1490 (s), 1414 (s), 1290
(m), 690 (s), 590 (s).
X-r a y Da t a Collect ion a n d St r u ct u r e Det er m in a -
tion . Suitable crystals of complexes 1-3 were selected and
sealed in a thin-walled glass capillaries for X-ray structure
analyses. The diffraction data were collected at room temper-
ature on a Bruker SMART 1000 diffractometer using graphite-
monochromated Mo KR (λ ) 0.71073 Å) radiation. Intensity
data were corrected for Lorentz-polarization and empirical
absorption effects. A summary of crystallographic data is given
in Table 1.
(10) Sheldrick, G. M. SHELX97, Package for Crystal Structure
Solution and Refinement; University of Go¨ttingen: Germany, 1997.
(11) Tilley, T. D.; Andersen, R. A.; Zalkin, A.; Templeton, D. H. Inorg.
Chem. 1982, 21, 2644.
(12) (a) Edelmann, F. T.; Rieckhoff, M.; Haiduc, I.; Silaghi-Dumi-
trescu, I. T. J . Organomet. Chem. 1993, 447, 203. (b) Wedler, M.;
Recknagel, A.; Edelmann, F. T. J . Organomet. Chem. 1990, 395, C26.
(13) Vicente, J .; Chicote, M. T.; Gonza´lez-Herrero, P.; J ones, P. G.
J . Chem. Soc., Chem. Commun. 1995, 745.
(14) Brouwer, E. B.; Legzdins, P.; Rettig, S. J .; Ross, K. J . Organo-
metallics 1993, 12, 4234.
(15) Chang, C. C.; Chen, J . H.; Srinivas, B.; Chiang, M. Y.; Lee, G.
H.; Peng, S. M. Organometallics 1997, 16, 4980.
The structures were solved by direct methods and refined
with full-matrix least squares on F2. All computations were

Notes
Organometallics, Vol. 21, No. 12, 2002 2531
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for Com p lex 1a
Y(1)-C(1)
Y(1)-C(3)
Y(1)-C(5)
Y(1)-C(8)
Y(1)-C(10)
Y(1)-S(1)
Y(2)-S(3)
S(1)-C(25)
S(3)-C(38)
Y(1)-Cp(1)
Y(2)-Cp(3)
2.618(6)
2.646(6)
2.659(6)
2.647(5)
2.653(5)
2.8595(14)
2.9023(15)
1.737(5)
1.729(5)
2.365(2)
2.390(2)
Y(1)-C(2)
Y(1)-C(4)
Y(1)-C(7)
Y(1)-C(9)
Y(1)-C(11)
Y(1)-S(2)
Y(2)-S(4)
S(2)-C(25)
S(4)-C(38)
Y(1)-Cp(2)
Y(2)-Cp(4)
2.634(6)
2.655(7)
2.692(5)
2.608(5)
2.710(5)
2.8754(16)
2.8659(15)
1.704(5)
1.697(5)
2.376(2)
2.395(2)
S(1)-Y(1)-S(2)
Y(1)-S(1)-Y(2)
61.93(4) S(4)-Y(2)-S(3)
102.84(4) Y(2)-S(3)-Y(1)
61.56(4)
99.36(4)
Cp(3)-Y(2)-Cp(4) 125.1(2)
Cp(1)-Y(1)-Cp(2) 125.3(2)
a
Cp(1) represents the centroid of C(1)-C(5) ring; Cp(2) repre-
sents the centroid of C(7)-C(11) ring; Cp(3) represents the centroid
of C(13)-C(17) ring; Cp(4) represents the centroid of C(19)-C(23)
ring.
F igu r e 1. ORTEP diagram of the molecular structure of
[(CH3C5H4)2Y(η2-S2CNPh2)]2‚CH3C6H5 (1).
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for Com p lex 2a
Yb(1)-C(1)
Yb(1)-C(2)#1
Yb(1)-C(3)#1
Yb(1)-C(6)
Yb(1)-C(7)
Yb(1)-S(1)
S(1)-C(9)
2.608(14)
2.591(11)
2.534(12)
2.570(11)
2.542(12)
2.695(3)
1.716(6)
1.341(15)
2.283(7)
Yb(1)-C(2)
Yb(1)-C(3)
Yb(1)-C(5)
Yb(1)-C(6)#1
Yb(1)-C(7)#1
Yb(1)-S(1)#1
C(9)-S(1)#1
Yb(1)-Cp(1)
2.591(11)
2.534(12)
2.620(16)
2.570(12)
2.542(12)
2.695(3)
1.716(6)
2.286(7)
N(1)-C(9)
Yb(1)-Cp(2)
S(1)-Yb(1)-S(1)#1
S(1)#-C(9)-S(1)
67.63(14) Cp(1)-Yb(1)-Cp(2) 134.3(7)
121.9(6)
a
Cp(1) represents the centroid of C(1)-C(3A) ring; Cp(2)
represents the centroid of C(5)-C(7A) ring.
F igu r e 2. ORTEP diagram of the molecular structure of
[(CH3C5H4)2Yb(η2-S2CNPh2)] (2).
Y(2), S(3), C(38), and S(4) form an interlinked tricycle
via two bridged S atoms. The bridged Y-S bonds are
asymmetric, and their lengths are 2.8595(14) Å for
Y(1)-S(1), 3.033(1) Å for Y(1)-S(3), 2.931(1) Å for Y(2)-
S(1), and 2.9023(15) Å for Y(2)-S(3), respectively, giving
an average of 2.932 Å, which is somewhat longer than
that of the terminal Y-S bond length (2.871 Å). This is
reasonable because the bridged bond length is normally
longer than that of the terminal bond. The C-S bond
distances in 1 are intermediate between single- and
double-bond distances.18 These parameters show that
the electrons are delocalized over the YS2C four-member
ring, which supports the structure proposed on the basis
of the analytical and spectral data. The average Y-C(Cp)
distance, 2.6522 Å, is in the range of values found in
other ytterbocene complexes, [(MeC5H4)2Y(µ-OPr-i)]2,
2.6662 Å;16 [(MeC5H4)2Y(µ-OCHdCH2)]2, 2.651 Å;17
(MeC5H4)2Y(THF)[OCN(Pr-i)2NPh], 2.674 Å.8
The coordination polyhedron formed in complex 2 has
previously been observed in (Me5C5)2Yb(S2CNEt2),11
although the mode of formation for complex 2 is novel.
There is the expected pattern of delocalization within
the YbS2C ring. The dithiocarbamate group is sym-
metrically coordinated to ytterbium, and the Yb-S and
S-C bond lengths (2.695(3), 1.716(6) Å) are comparable
with those found in (Me5C5)2Yb(S2CNEt2) (2.70(1),
1.71(1) Å), respectively.11
derivatives (Me5C5)2Ln(S2CNEt2) (Ln ) Yb, Nd) and
(Me5C5)2Nd(S2CNMe2) have been reported in the litera-
tures, the synthetic routes are quite different. The
former was formed via metathesis reaction of Na(OEt2)2-
(Me5C5)2LnCl2 with NaS2CNEt2,11 and the latter was
obtained by redox reaction of divalent neodymium
complex [(Me5C5)2NdCl2][K(THF)] with [Me2NC(S)S]2.12
To our knowledge, this is the first example of the
insertion reaction of CS2 into the Ln-N bond of orga-
nolanthanide amide.
2(CH3C5H4)2YNPh2(THF) + 2CS2 toluene8
[(CH3C5H4)2Y(S2CNPh2)]2‚CH3C6H5 (1)
(CH3C5H4)2YbNPh2(THF) + CS2 f
(CH3C5H4)2Yb(S2CNPh2) (2)
To understand the solid-state structures of these
complexes further, their single-crystal structures were
determined. The results show that complex 1 is a dimer,
while complex 2 exists as a monomer. The molecular
structures are shown in Figures 1 and 2, and selected
bond distances and angles are listed in Tables 2 and 3,
respectively.
Complex 1 is composed of two [(CH3C5H4)2Y(S2-
CNPh2)] units linked by two sulfur atoms, and the
central metal Y is coordinated by two CH3C5H4 rings
and three S atoms to give the formal coordination
number of nine. The eight atoms Y(1), S(2), C(25), S(1),
(16) Li, H.; Yao, Y.; Shen, Q.; Weng, L. Acta Crystallogr. 2000, C56,
747.
(17) Evans, W. J .; Dominguez, R.; Hanuse, T. P. Organometallics
1986, 5, 1291.
(18) Hafelinger, G. Chem. Ber. 1970, 103, 2920.

2532 Organometallics, Vol. 21, No. 12, 2002
Notes
Ta ble 4. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for Com p lex 3a
Y(1)-C(1)
Y(1)-C(3)
Y(1)-C(5)
Y(1)-C(8)
Y(1)-C(10)
Y(1)-S(1)
S(1)-Y(1)#1
N(1)-C(13)
Y(1)-Cp(2)
2.634(3)
2.614(3)
2.674(3)
2.603(3)
2.645(3)
2.7847(8)
3.1915(8)
1.304(3)
2.348(1)
Y(1)-C(2)
Y(1)-C(4)
Y(1)-C(7)
Y(1)-C(9)
Y(1)-C(11)
Y(1)-N(1)
S(1)-C(13)
Y(1)-Cp(1)
2.629(3)
2.648(3)
2.609(3)
2.621(3)
2.653(3)
2.445(8)
1.727(3)
2.359(1)
N(1)-Y(1)-S(1)
58.45(5) Cp(1)-Y(1)-Cp(2) 128.3(1)
Y(1)-S(1)-Y(1)#1 119.41(2) N(1)-C(13)-S(1)
115.31(19)
a
Cp(1) represents the centroid of C(1)-C(5) ring; Cp(2) repre-
sents the centroid of C(7)-C(11) ring.
F igu r e 3. ORTEP diagram of the molecular structure of
{(CH3C5H4)2Y[η2-SC(NPh2)NPh]}2 (3).
between the corresponding single- and double-bond
distances.18 These bond parameters indicate substantial
electronic delocalization over the S-C-N unit. The
observed Y(1)-N(1) (2.445(2) Å) bond distance is in
agreement with that of the Nd-N bond (2.534(4) Å) in
(CH3C5H4)2Nd[η2-SC(SPh)NPh](THF),20 if the difference
in ionic radii is considered. The average Y-S bond
distance, 2.988 Å, is longer than that of the Nd-S (2.881
Å) bond in (CH3C5H4)2Nd[η2-SC(SPh)NPh](THF),20 al-
though the ionic radius for Y3+ (1.075 Å) is smaller than
that for Nd3+ (1.163 Å).21 This can be attributed to the
formation of the bridged bond in complex 3. The
Y-C(Cp) distances range from 2.603(3) to 2.674(3) Å,
giving an average distance of 2.633(3) Å, which is
comparable to that in complex 1. The Cp(1)(centroid)-
Y-Cp(2)(centroid) angle in complex 3, 128.3(1)°, is
similar to those found in the following complexes,
[(MeC5H4)2Y(µ-OCHdCH2)]2, 128.1°;17 (MeC5H4)2Y-
(THF)[OCN(Pr-i)2NPh], 127.5°;8 [(C5H5)2Y(µ-Me)]2,
128.9°.22
Syn t h esis a n d Molecu la r St r u ct u r e of {(CH 3-
C5H 4)2Y[η2-SC(NP h 2)NP h ]}2 (3). The reaction of
(CH3C5H4)2YNPh2(THF) with PhNCS goes smoothly.
The insertion product, {(CH3C5H4)2Y[η2-SC(NPh2)-
NPh]}2 (3), which was identified by elemental analyses,
was isolated in good yield. In the IR spectrum of 3, the
two strong absorptions at 1490 and 1028 cm-1 can be
assigned to the bidentate CN and CS vibrations in the
N-phenylthioacetamide ligand, respectively,19 which
indicates that a new thioamido ligand, [SC(NPh2)NPh]-,
is formed by the transfer of the -NPh2 group to the
isothiocyanate carbon atom, as shown in eq 3.
2(CH3C5H4)2YNPh2(THF) + 2PhNCS f
{(CH3C5H4)2Y[η2-SC(NPh2)NPh]}2 (3)
The estimations from the IR spectrum have also been
unambiguously verified by X-ray crystal structure analy-
sis of 3.
Ack n ow led gm en t. We gratefully acknowledge the
Chinese National Natural Science Foundation, and the
Department of Education of J iangsu Province, for
financial support.
X-ray determination indicates that complex 3 has a
dimeric structure, as shown in Figure 3, in which two
(CH3C5H4)2Y fragments connect with two [SC(SPh)NPh]-
units. The six atoms Y(1), N(1), C(13), S(1), Y(1A),
N(1A), C(13A), and S(1A) form an interlinked tricyclic
structure via two bridged S atoms. Its coordination
geometry is similar to that in complex 1. Selected bond
distances and angles are given in Table 4.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal
data, atomic coordinates, anisotropic displacement parameters,
and bond lengths and angles for complexes 1-3. This material
is available free of charge via the Internet at http://pubs.acs.org.
OM0109509
The N(1)-C(13) and C(13)-S(1) bond lengths in
complex 3, 1.304(3) and 1.727(3) Å, are intermediate
(20) Shen, Q.; Li, H.; Yao, C.; Yao, Y.; Zhang, L.; Yu, K. Organo-
metallics 2001, 20, 3070.
(19) (a) Segerer, U.; Sieler, J .; Hey-Hawkins, E. Organometallics
2000, 19, 2445. (b) Mei, W.; Shiwei, L.; Meizhi, B.; Hefu, G. J .
Organomet. Chem. 1993, 447, 227.
(21) Shannon, R. D. Acta Crystallogr. 1976, A32: 751.
(22) Holton, J .; Lappert, M. F.; Ballard, D. G. H.; Pearce, R.; Atwood,
J . L.; Hunter, W. E. J . Chem. Soc., Dalton Trans. 1979, 54.