σ Bond metathesis reactivity of allyl scandium metallocenes with diphenyldichalcogenides, PhEEPh (E = S, Se, Te)

Article abstract of DOI:10.1021/om2001876

The σ bond metathesis reactivity of (C₅Me ₄H)₃Sc, which has a (n₅-C₅Me ₄H)₂Sc(n₁-C₅Me₄H) structure in the solid state, has been investigated and compared with that of a conventional (C₅Me₄H)^- metallocene complex, (C₅Me₄H)₂Sc(n₃-C₃H ₅), 1. Complex 1 reacts with PhEEPh (E = S, Se, Te) in toluene to form the σ bond metathesis products (C₃H₅)EPh and [(C₅Me₄H)2Sc(SPh)]2, (C₅Me₄H) ₂Sc(SePh), and (C₅Me₄H)₂Sc(TePh), respectively. Analogous reactions in toluene/THF generate the THF solvates (C₅Me₄H)₂Sc(EPh)(THF). The monometallic sulfur derivative (C₅Me₄H)₂Sc(Spy-κ²- S,N) forms from the reaction of 1 with 2,2'- dipyridyl disulfide, pySSpy. (C₅Me₄H)₃Sc reacts similarly, showing that the (n₁-C₅Me₄H)^- solid-state structure yields Sc-C bond reactivity in solution.

Full text of DOI:10.1021/om2001876

ARTICLE
pubs.acs.org/Organometallics
σ Bond Metathesis Reactivity of Allyl Scandium Metallocenes with
Diphenyldichalcogenides, PhEEPh (E = S, Se, Te)
Selvan Demir, Thomas J. Mueller, Joseph W. Ziller, and William J. Evans*
Department of Chemistry, University of California, Irvine, California 92697-2025, United States
S Supporting Information
b
ABSTRACT:
The σ bond metathesis reactivity of (C5Me4H)3Sc, which has a (η5-C5Me4H)2Sc(η1-C5Me4H) structure in the solid state, has been
investigated and compared with that of a conventional (C5Me4H)ꢀ metallocene complex, (C5Me4H)2Sc(η3-C3H5), 1. Complex 1
reacts with PhEEPh (E = S, Se, Te) in toluene to form the σ bond metathesis products (C3H5)EPh and [(C5Me4H)2Sc(SPh)]2,
(C5Me4H)2Sc(SePh), and (C5Me4H)2Sc(TePh), respectively. Analogous reactions in toluene/THF generate the THF solvates
(C5Me4H)2Sc(EPh)(THF). The monometallic sulfur derivative (C5Me4H)2Sc(Spy-κ2-S,N) forms from the reaction of 1 with 2,20-
dipyridyl disulfide, pySSpy. (C5Me4H)3Sc reacts similarly, showing that the (η1-C5Me4H)ꢀ solid-state structure yields ScꢀC bond
reactivity in solution.
’ INTRODUCTION
cases, but (C5Me5)EPh, the byproduct of σ bond metathesis,
eq 2, was the major byproduct in other reactions.13 σ Bond
The synthesis of sterically crowded complexes containing
three pentamethylcyclopentadienyl rings, (η5-C5Me5)3M (M =
Ln, Y, U), demonstrated that it was possible to make a series of
complexes in which all the metal ligand bonds are longer than
those previously observed.1ꢀ6 Not only are these compounds
unusual synthetically and structurally, but they also display
unique reactivity. The long MꢀC(C5Me5) bonds translate into
high reactivity and demonstrate a method to activate the
normally inert (η5-C5Me5)ꢀ groups extensively used as ancillary
ligands. Until recently, three general types of unexpected
(C5Me5)ꢀ reactivity have been observed with these sterically
crowded (C5Me5)3M complexes depending on the substrate: (a)
η1-like (C5Me5)ꢀ reactivity;3,6ꢀ8 (b) a one-electron reduction
process called sterically induced reduction (SIR);3,9,10 and (c)
displacement of pentahapto (η5-C5Me5)ꢀ by a ligand of lower
hapticity.11,12 Each of these reactions typically gives a single
product in high yield.
Recently, it was observed that in reactions with diphenyldi-
chalcogenide substrates, PhEEPh (E = S, Se, Te), the (C5-
Me5)3M complexes could react along two pathways.13 These
reactions formed a single type of metallocene product,
[(C5Me5)2M(EPh)]2, but mixtures of two types of byproducts
were observed depending on M and E. (C5Me5)2, the byproduct
of sterically induced reduction, eq 1, was predominant in some
2ðC5Me5Þ3M þ 2PhEEPh f ½ðC5Me5Þ2MðEPhÞꢁ2
E¼S, Se
þ ðC5Me5ÞEPh þ ðC5Me5Þ2 ð2Þ
major
minor
metathesis could occur via a pseudoalkyl intermediate,
(η5-C5Me5)2M(η1-C5Me5), but no crystallographic evidence
for such a structure had been observed even in base adduct
species, (C5Me5)3ML14ꢀ16 and (C5Me5)3ML2.12,16 Although σ
bond metathesis is well established with substrates that can put H
or Si in the position diagonal to the metal,17ꢀ22 reactions with
chalcogens in the diagonal position are not so common.13,23,24
Recently, the first structurally characterizable example of a
(η5-C5R5)2Ln(η1-C5R5) complex (Ln = rare earth, i.e., Sc, Y,
lanthanide) was discovered with the combination of Sc3þ and
(C5Me4H)ꢀ, namely, (η5-C5Me4H)2Sc(η1-C5Me4H).25 This
complex provided the first chance to test σ bond metathesis
reactivity in a tris(polyalkylcyclopentadienyl) complex with
demonstrated access to a (η1-C5Me4H)ꢀ binding mode. How-
ever, the viability of σ bond metathesis of PhEEPh with more
conventional scandium alkyl complexes had not yet been
established.
This present study was initiated to remedy this deficiency and
to provide information on σ bond metathesis between ScꢀC and
2ðC5Me5Þ3M þ PhTeTePh f ½ðC5Me5Þ2MðTePhÞꢁ2 þ ðC5Me5Þ2
ð1Þ
Received: February 28, 2011
Published: May 09, 2011
r
2011 American Chemical Society
3083
dx.doi.org/10.1021/om2001876 Organometallics 2011, 30, 3083–3089
|

Organometallics
ARTICLE
PhEEPh in a conventional (C5Me4H)ꢀ metallocene complex.
Reactions with (C5Me4H)2Sc(η3-C3H5), 1,26 were studied be-
cause it is the only hydrocarbyl scandium (C5Me4H)ꢀ metallo-
cene complex in the literature and also because allyl complexes of
lanthanide metallocenes have proven to be conveniently synthe-
sized, reliable sources of MꢀC bond reactivity.27ꢀ32 The reactiv-
ity of 1 with PhEEPh is reported here and compared to the
reactivity of (η5-C5Me4H)2Sc(η1-C5Me4H).
MHz, benzene-d6): δ 8.21 (m, 2H, C6H5), 7.09 (m, 3H, C6H5), 6.59
(s, 2H, C5Me4H), 2.04 (s, 12H, C5Me4H), 1.48 (s, 12H, C5Me4H).
13C NMR (126 MHz, benzene-d6): δ 142.8 (C6H5), 129.3 (C6H5),
126.1 (C6H5), 125.6 (C5Me4H), 121.7 (C5Me4H), 118.3 (C5Me4H),
115.3 (C6H5), 13.1 (C5Me4H), 12.5 (C5Me4H). IR: 3105w, 3070w,
3056m, 3037w, 2974m, 2900s, 2859s, 2724m, 2660m, 1640w, 1596w,
1571s, 1469s, 1433s, 1385s, 1373s, 1323m, 1297w, 1260w, 1113w,
1061m, 1018s, 991m, 836vs, 822s, 733vs, 694s, 652w, 628w,
614m cmꢀ1. Anal. Calcd for C24H31ScTe: C, 58.58; H, 6.35. Found:
C, 58.28; H, 6.29.
’ EXPERIMENTAL SECTION
(C5Me4H)2Sc(SPh)(THF), 5. In a nitrogen-filled glovebox, PhSSPh
(0.072 g, 0.33 mmol) was added to a yellow solution of 1 (0.108 g, 0.33
mmol) in toluene (10 mL) and THF (0.1 mL). After the mixture was
stirred for 24 h, the solution was evaporated to dryness to yield a yellow-
The manipulations described below were conducted under argon or
nitrogen with rigorous exclusion of air and water using Schlenk, vacuum
line, and glovebox techniques. Solvents were sparged with UHP argon
and dried over columns containing Q-5 and molecular sieves. NMR
solvents (Cambridge Isotope Laboratories) were dried over sodiumꢀ
potassium alloy, degassed by three freezeꢀpumpꢀthaw cycles, and
vacuum-transferred before use. PhEEPh (E = S, Se, Te) and 2,20-
dipyridyl disulfide (pySSpy) were purchased from Aldrich and sublimed
prior to use. (C5Me4H)2Sc(η3-C3H5), 1,26 and (η5-C5Me4H)2Sc(η1-
1
white, tacky residue of 5 and (C3H5)SPh (identified by H NMR).33
Both compounds are soluble in hexane. Colorless crystals of 5 (0.107 g,
69%) suitable for X-ray analysis were grown from hexane at ꢀ35 °C. 1H
NMR (500 MHz, benzene-d6): δ 7.66 (d, 2H, C6H5), 7.23 (m, 2H,
C6H5), 7.04 (m, 1H, C6H5), 5.95 (s, 2H, C5Me4H), 1.96 (s, 12H,
C5Me4H), 1.91 (s, 12H, C5Me4H). 13C NMR (126 MHz, benzene-d6): δ
151.5 (C6H5), 137.2 (C6H5), 128.9 (C6H5), 123.5 (C6H5), 122.7
(C5Me4H), 119.0 (C5Me4H), 115.6 (C5Me4H), 13.6 (C5Me4H), 12.7
(C5Me4H). IR: 3090w, 3070w, 2968m, 2906m, 2861m, 2722w, 1580m,
1567w, 1509w, 1471s, 1450m, 1434m, 1373m, 1337w, 1295w, 1240w,
1177w, 1146w, 1111w, 1087s, 1064m, 1015s, 949w, 923m, 861s, 837s,
800s, 735vs, 699s, 690s, 619m cmꢀ1. Anal. Calcd for C28H39OScS: C,
71.76; H, 8.39. Found: C, 71.35; H, 8.88.
C5Me4H)25 were prepared according to literature methods. 1H and 13
C
NMR spectra were recorded on a Bruker DRX500 spectrometer at
25 °C. Infrared spectra were recorded as KBr pellets on a Varian 1000
FTIR spectrophotometer at 25 °C. Elemental analyses were performed
on a PerkinElmer 2400 Series II CHNS analyzer. Mass spectrometry
analyses were performed on a Thermo Trace MSþ GC-MS.
[(C5Me4H)2Sc(μ-SPh)]2, 2. In an argon-filled glovebox, PhSSPh
(0.099 g, 0.45 mmol) was added to a stirred yellow solution of
(C5Me4H)2Sc(η3-C3H5), 1 (0.149 g, 0.454 mmol), in toluene
(10 mL). After 24 h, the solution was evaporated to dryness to yield a
yellow powder. This was washed with a small amount of cold (ꢀ35 °C)
(C5Me4H)2Sc(SePh)(THF), 6. As described for 5, the reaction of
PhSeSePh (0.078 g, 0.25 mmol) and 1 (0.082 g, 0.25 mmol) in toluene
(10 mL) and THF (0.1 mL) yields a yellow-white, tacky residue of 6 and
(C3H5)SePh.34 Since 6 is only slightly soluble in hexane, the product was
washed with a minimal amount of cold hexane (ꢀ35 °C) to remove
(C3H5)SePh. Colorless crystals of 6 (0.081 g, 63%) suitable for X-ray
1
hexane in order to remove (C3H5)SPh33 (identified by H NMR and
1
mass spectroscopy) and give yellow crystalline 2 (0.140 g, 78%). H
1
analysis were grown from toluene at ꢀ35 °C. H NMR (500 MHz,
NMR (500 MHz, benzene-d6): δ 7.65 (d, 2H, C6H5), 7.20 (m, 2H,
C6H5), 7.03 (m, 1H, C6H5), 6.23 (s, 2H, C5Me4H), 2.08 (s, 12H,
C5Me4H), 1.57 (s, 12H, C5Me4H). 13C NMR (126 MHz, benzene-d6): δ
157.3 (C6H5), 134.1 (C6H5), 126.0 (C6H5), 125.6 (C6H5), 124.2
(C5Me4H), 121.0 (C5Me4H), 118.3 (C5Me4H), 12.5 (C5Me4H), 12.3
(C5Me4H). IR: 3071w, 3058w, 2966m, 2908m, 2860m, 2726w, 1575s,
1555m, 1475s, 1437s, 1382m, 1328w, 1297w, 1252m, 1178w, 1154w,
benzene-d6): δ 7.89 (d, 2H, C6H5), 7.17 (m, 2H, C6H5), 7.08 (m, 1H,
C6H5), 6.15 (s, 2H, C5Me4H), 3.61 (s, 8H, C4H8O), 2.00 (s, 12H,
C5Me4H), 1.77 (s, 12H, C5Me4H), 1.26 (s, 8H, C4H8O). 13C NMR (126
MHz, benzene-d6): δ 141.7 (C6H5), 137.0 (C6H5), 128.8 (C6H5), 124.6
(C6H5), 123.5 (C5Me4H), 119.9 (C5Me4H), 116.5 (C5Me4H)), 72.8
(C4H8O), 25.9 (C4H8O), 13.3 (C5Me4H), 12.7 (C5Me4H). IR: 3112w,
3062w, 2970m, 2909m, 2860m, 2729m, 1644w, 1575s, 1470s, 1435s,
1450s, 1384s, 1372s, 1325w, 1242w, 1176w, 1112w, 1070s, 1022s,
1012s, 925m, 905m, 857s, 841s, 824s, 809s, 738vs, 695s, 667m,
615m cmꢀ1. Anal. Calcd for C28H39OScSe: C, 65.23; H, 7.63. Found:
C, 64.81; H, 7.30.
1072m, 1022s, 996m, 901m, 834s, 794s, 738s, 701m, 688s, 613m cmꢀ1
.
Anal. Calcd for C48H62S2Sc2: C, 72.70; H, 7.88. Found: C, 72.97; H,
7.73. Yellow crystals of 2 suitable for X-ray analysis were grown from a
saturated toluene solution in the glovebox at ꢀ35 °C.
(C5Me4H)2Sc(SePh), 3. As described for 2, complex 3 was obtained
as a colorless crystalline solid (0.161 g, 76%), and (C3H5)SePh34 was
isolated from the reaction of PhSeSePh (0.148 g, 0.465 mmol) with 1
(0.156 g, 0.475 mmol) in toluene (10 mL). Colorless crystals of 3
suitable for X-ray analysis were grown from toluene at ꢀ35 °C. 1H NMR
(500 MHz, benzene-d6): δ 7.91 (d, 2H, C6H5), 7.15 (m, 2H, C6H5),
7.07 (m, 1H, C6H5), 6.35 (s, 2H, C5Me4H), 2.08 (s, 12H, C5Me4H),
1.53 (s, 12H, C5Me4H). 13C NMR (126 MHz, benzene-d6): δ 140.7
(C6H5), 137.0 (C6H5), 129.0 (C6H5), 125.5 (C5Me4H), 125.1 (C6H5),
121.3 (C5Me4H), 118.5 (C5Me4H), 12.6 (C5Me4H), 12.3 (C5Me4H).
IR: 3112w, 3072w, 3060w, 3043w, 2976m, 2901m, 2860m, 2728w,
1664w, 1575s, 1470s, 1449s, 1435s, 1385s, 1372s, 1323m, 1176w,
1156m, 1114w, 1071s, 1061m, 1024s, 998m, 975w, 943w, 904w,
842vs, 824vs, 738vs, 694s, 667m, 629w, 615m cmꢀ1. Anal. Calcd for
C24H31ScSe: C, 65.01; H, 7.05. Found: C, 64.90; H, 7.55.
(C5Me4H)2Sc(TePh)(THF), 7. As described for 5, the reaction of
PhTeTePh (0.299 g, 0.730 mmol) and 1 (0.240 g, 0.731 mmol)
in toluene (10 mL) and THF (0.1 mL) gave 7 as a colorless crystalline
solid (0.267 g, 65%) and (C3H5)TePh.35 Colorless crystals of 7 suitable
for X-ray analysis were grown from benzene at 25 °C. 1H NMR
(500 MHz, benzene-d6): δ 8.19 (m, 2H, C6H5), 7.09 (m, 3H, C6H5),
6.36 (s, 2H, C5Me4H), 3.58 (s, 4H, C4H8O), 1.97 (s, 12H, C5Me4H),
1.70 (s, 12H, C5Me4H), 1.29 (s, 4H, C4H8O). 13C NMR (126 MHz,
benzene-d6): δ 142.8 (C6H5), 129.0 (C6H5), 125.7 (C6H5), 123.6
(C5Me4H), 120.2 (C5Me4H), 116.4 (C5Me4H), 116.0 (C6H5),
71.4 (C4H8O), 25.9 (C4H8O), 13.4 (C5Me4H), 13.1 (C5Me4H). IR:
3103w, 3061w, 3048w, 2970s, 2941s, 2906s, 2860s, 2724w, 1571s,
1470s, 1450s, 1430s, 1381m, 1337w, 1293w, 1240w, 1173w, 1150w,
1109w, 1061w, 1016s, 924w, 858s, 831s, 817s, 734vs, 696s, 652w,
616w cmꢀ1. Anal. Calcd for C28H39OScTe: C, 59.61; H, 6.97. Found:
C, 59.26; H, 6.87.
(C5Me4H)2Sc(TePh), 4. As described for 2, complex 4 was obtained
as a yellow crystalline solid (0.101 g, 73%), and (C3H5)TePh35 was
isolated from the reaction of PhTeTePh (0.115 g, 0.281 mmol) and 1
(0.092 g, 0.028 mmol) in toluene (10 mL). Yellow crystals of 4 suitable
for X-ray analysis were grown from toluene at ꢀ35 °C. 1H NMR (500
(C5Me4H)2Sc(Spy-K2-S,N), 8. In a nitrogen-filled glovebox, 2,20-
dipyridyl disulfide, pySSpy (0.097 g, 0.44 mmol), was added at ꢀ35 °C
to a precooled (ꢀ35 °C), stirred yellow solution of 1 (0.144 g, 0.438
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Organometallics
ARTICLE
Scheme 1. Reactivity of (C5Me4H)2Sc(η3-C3H5), 1, with PhEEPh
1
mmol) in toluene (10 mL). The reaction mixture was allowed to warm
to ambient temperature. After the mixture was stirred for 24 h, the
solution was evaporated to dryness to yield a yellow-white, tacky residue
of 8 and (C3H5)Spy.36 The product was washed with cold hexane
(ꢀ35 °C) to remove (C3H5)Spy and dried under vacuum to yield 8, as a
colorless solid (0.137 g, 79%). 1H NMR (500 MHz, benzene-d6): δ 7.19
(m, 2H, C5H4N), 6.66 (m, 1H, C5H4N), 6.15 (m, 1H, C5H4N), 6.02, (s,
1H, C5Me4H), 1.99 (s, 6H, C5Me4H), 1.91 (s, 6H, C5Me4H), 1.86 (s,
6H, C5Me4H), 1.41 (s, 6H, C5Me4H). 13C NMR (126 MHz, benzene-
d6): δ 145.4 (C4H4NCS), 136.4, (C4H4NCS), 123.8 (C5Me4H), 121.5
(C5Me4H), 119.3 (C5Me4H), 117.2 (C5Me4H), 115.2 (C4H4NCS),
112.1 (C5Me4H), 14.2 (C5Me4H), 13.9 (C5Me4H), 12.7 (C5Me4H),
11.2 (C5Me4H). Two of the carbon atoms of the pyridyl ring, including
the quaternary carbon, could not be unambiguously assigned in the 13C
NMR spectrum. IR: 3092w, 3077w, 3060w, 3044w, 2962m, 2934m,
2903m, 2860m, 2721w, 2660w, 1731w, 1591vs, 1538s, 1479w, 1447s,
1413vs, 1380s, 1368s, 1326m, 1263m, 1183m, 1136vs, 1086m, 1022m,
1003m, 986w, 868w, 802s, 756vs, 728s, 644m, 617m cmꢀ1. Anal. Calcd
for C23H30NSSc: C, 69.49; H, 7.61; N, 3.52. Found: C, 69.22; H, 7.54;
N, 3.53. Colorless crystals of 8 suitable for X-ray analysis were grown
from benzene at 25 °C.
4 and (C5Me4H)TePh.37 (C5Me4H)2 was not observed by H NMR
spectroscopy or by GC-MS.
’ RESULTS
Reactivity of (C5Me4H)2Sc(η3-C3H5), 1, with PhEEPh (E = S,
Se, Te). (C5Me4H)2Sc(η3-C3H5), 1, reacts with PhSSPh to form
the dimeric arylsulfide complex [(C5Me4H)2Sc(SPh)]2, 2, and
with PhSeSePh and PhTeTePh to form the monomeric analo-
gues (C5Me4H)2Sc(SePh), 3, and (C5Me4H)2Sc(TePh), 4,
respectively, Scheme 1. In each case, (C3H5)EPh was isolated
as a byproduct. For E = S and Se, the (C3H5)EPh compounds33,34
were characterized by NMR and mass spectroscopy. The less
stable (C3H5)TePh35 was characterized by NMR spectroscopy.
Complexes 2ꢀ4 were isolated in crystalline form in at least 60%
yield and were characterized by X-ray crystallography, Table 1.
Complexes 2 and 4 are shown in Figures 1 and 2, respectively, and
structural details are discussed below.
When the reaction of 1 with PhEEPh is performed in the
presence of THF, the monomeric THF adducts (C5Me4-
H)2Sc(EPh)(THF) (E = S, 5; Se, 6; Te, 7) are isolated, eq 3,
and (C3H5)EPh is again observed as a byproduct. Each solvated
scandium complex was isolated in over 60% yield and character-
ized by X-ray crystallography, Table 2. Complex 5 is shown in
Figure 3 as a representative example of 5ꢀ7.
[(C5Me4H)2Sc(μ-SPh)]2, 2,from(η5-C5Me4H)2Sc(η1-C5Me4H),
9. In a nitrogen-filled glovebox, PhSSPh (0.020 g, 0.092 mmol) was added
to a stirred orange solution of 9 (0.037 g, 0.091 mmol) in toluene (5 mL).
After 5 d, the pale yellow solution was evaporated to dryness to yield a tacky,
yellow solid, which was washed with a minimal amount (∼0.5 mL) of
cold hexane (ꢀ30 °C) to yield 2 as a very pale yellow powder (34 mg,
95%), as confirmed by 1H NMR spectroscopy. The hexane washing
was evaporated to dryness to yield a tacky, pale yellow solid (22 mg),
1
which by H NMR spectroscopy contained a small amount of 2 and
(C5Me4H)SPh.37 (C5Me4H)2 was not observed by 1H NMR spectroscopy
or by GC-MS.
(C5Me4H)2Sc(SePh), 3, from (η5-C5Me4H)2Sc(η1-C5Me4H),
9. In a nitrogen-filled glovebox, PhSeSePh (0.028 g, 0.090 mmol)
was added to a stirred orange solution of 9 (0.036 g, 0.088 mmol) in
toluene (4 mL). After 24 h, the pale yellow solution was evaporated
to dryness to yield a tacky, yellow solid, which was washed with a
minimal amount (∼0.5 mL) of cold hexane (ꢀ30 °C) to yield 3 as a
Consistent with the formation of the THF adducts 5ꢀ7, a
pyridyl analogue, (C5Me4H)2Sc(Spy-κ2-S,N), 8, was obtained
from the reaction of (C5Me4H)2Sc(η3-C3H5) with 2,20-dipyridyl
disulfide, pySSpy, eq 4. A 79% yield was observed, and the
expected σ bond metathesis byproduct, (C3H5)Spy,36 was iso-
lated. The X-ray crystal structure of 8 is shown in Figure 4.
1
very pale yellow powder (24 mg, 61%), as confirmed by H NMR
spectroscopy. The hexane washing was evaporated to dryness to
1
yield a tacky, pale yellow solid (40 mg), which by H NMR spectros-
copy contained a small amount of additional 3 and (C5Me4H)SePh.37
(C5Me4H)2 was not observed by 1H NMR spectroscopy or by
GC-MS.
(C5Me4H)2Sc(TePh), 4, from (η5-C5Me4H)2Sc(η1-C5Me4H),
9. In a nitrogen-filled glovebox, PhTeTePh (0.041 g, 0.10 mmol) was
added to a stirred orange solution of 9 (0.040 g, 0.098 mmol) in toluene
(4 mL). After 24 h, the orange solution was evaporated to dryness to
yield a tacky, orange solid, which was washed with a minimal amount
(∼0.5 mL) of cold hexane (ꢀ30 °C) to yield 4 as a yellow powder
Structural Analysis. [(C5Me4H)2Sc(EPh)]x, 2ꢀ4. [(C5Me4-
H)2Sc(SPh)]2, 2 (Figure 1), crystallizes as a dimer in which
each metal is formally eight coordinate. This dimeric structure is
common for rare earth metallocene complexes, and the structure
1
(27 mg, 56%), as confirmed by H NMR spectroscopy. The hexane
washing was evaporated to dryness to yield a tacky, orange solid (52 mg),
which by 1H NMR spectroscopy contained a small amount of additional
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Organometallics
Table 1. X-ray Data Collection Parameters for [(C5Me4H)2Sc(SPh)]2, 2, (C5Me4H)2Sc(SePh), 3, and (C5Me4H)2Sc(TePh), 4
ARTICLE
2
3
4
empirical formula
fw
C
48H62S2Sc2 C7H8
C24H31ScSe C7H8
C24H31ScTe C7H8
3
3
3
885.15
143(2)
monoclinic
P21/n
535.54
148(2)
orthorhombic
Pnma
584.18
143(2)
orthorhombic
Pnma
temperature (K)
cryst syst
space group
a (Å)
9.1827(5)
15.5610(8)
16.4433(9)
90
11.2833(5)
11.7599(6)
19.9881(10)
90
11.5128(11)
11.8430(11)
20.2121(19)
90
b (Å)
c (Å)
R (deg)
β (deg)
98.9859(6)
90
90
90
γ (deg)
90
90
volume (Å3)
2320.8(2)
2
2652.2(2)
4
2755.8(4)
4
Z
F
calcd (Mg/m3)
μ (mmꢀ1
1.267
1.341
1.408
)
0.419
1.667
1.321
R1 [I > 2.0σ(I)]a
wR2 (all data)a
0.0346
0.0469
0.1570
0.0406
0.1340
0.0963
2 2
a Definitions: wR2 = [∑[w(Fo ꢀ Fc2)2]/∑[w(Fo ) ] ]1/2, R1 = ∑ Fo| ꢀ |Fc /∑|Fo|.
2
Table 2. X-ray Data Collection Parameters for
(C5Me4H)2Sc(SPh)(THF), 5, (C5Me4H)2Sc(SePh)(THF), 6,
(C5Me4H)2Sc(TePh)(THF), 7, and (C5Me4H)2Sc(Spy-κ2-S,
N), 8
5
6
7
8
empirical formula C28H39OSSc C28H39OScSe C28H39OScTe C23H30NSSc
fw
468.61
515.51
148(2)
triclinic
P1
8.8672(5)
9.7827(6)
564.15
93(2)
triclinic
P1
9.3570(3)
16.8480(6)
18.5223(6)
67.1803(4)
397.50
93(2)
monoclinic
P21/c
16.3661(5)
8.4809(3)
15.8932(5)
90
108.00
90
2097.98(12)
4
1.258
0.457
0.0304
0.0841
temperature (K) 148(2)
cryst syst
space group
a (Å)
b (Å)
c (Å)
triclinic
P1
8.9008(4)
9.4443(5)
15.9737(8) 15.3323(9)
81.1952(5) 94.6992(7)
75.3670(5) 102.8106(7) 79.3325(4)
71.1870(5) 97.2083(7) 76.4365(4)
1226.05(10) 1278.34(13) 2601.89(15)
Figure 1. ORTEP44 of [(C5Me4H)2Sc(SPh)]2, 2, drawn at the 50%
probability level. Hydrogen atoms and toluene solvent molecule are
omitted for clarity.
R (deg)
β (deg)
γ (deg)
volume (Å3)
Z
2
2
4
F
calcd (Mg/m3)
μ (mmꢀ1
1.269
0.403
1.339
1.729
0.0248
0.0681
1.440
1.399
0.0217
0.0549
)
R1 [I > 2.0σ(I)]a 0.0302
wR2 (all data)a
0.0817
a Definitions: wR2 = [∑[w(Fo ꢀ Fc2)2]/∑[w(Fo ) ] ]1/2, R1 = ∑ Fo| ꢀ
2
2 2
|Fc /∑|Fo|.
(C5Me5)ꢀ ligands. The hydrogen-substituted ring carbons in each
metallocene in 2 are almost perfectly staggered: the two HCꢀ(ring
centroid)ꢀSc planes have a dihedral angle of 1.5°. The plane
defined by the six carbon atoms in the aryl ring of 2 is twisted 38.0°
from the plane defined by the two scandium and two sulfur atoms,
larger than that observed in [(C5Me5)2Y(SPh)]2,38 20.1°, and
[(C5Me5)2Sm(SPh)]2,39 21.5°. This suggests there is more crowd-
ing in 2.
The isolation of (C5Me4H)2Sc(SePh), 3, and (C5Me4H)2-
Sc(TePh), 4, as monomers in contrast to dimer 2 can be
rationalized by the difference in size of the chalcogens. Two Se
or Te donor atoms may be too large for the small scandium
even in the tetramethylcyclopentadienyl [(C5Me4H)2Sc]þ
unit. On the other hand, in the series (pyridine)4Yb(SPh)2,
Figure 2. ORTEP of (C5Me4H)2Sc(TePh), 4, drawn at the 50%
probability level. Hydrogen atoms and toluene solvent molecule are
omitted for clarity. (C5Me4H)2Sc(SePh), 3, is isomorphous (see
Supporting Information).
38
of 2 is similar to that of [(C5Me5)2Y(SPh)]2 and [(C5-
Me5)2Sm(SPh)]239 when the differences in ionic radii40 are taken
into account, Table 3. A similar structure with the much smaller
scandium is probably possible since 2 contains (C5Me4H)ꢀ and not
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Table 3. Selected Bond Distances (Å) and Angles (deg) for
[(C5Me4H)2Sc(μ-SPh)]2, 2, [(C5Me5)2Y(μ-SPh)]2, and
[(C5Me5)2Sm(μ-SPh)]2, Along with Their Eight-Coordinate
M3þ Ionic Shannon Radii40
Sc, 2
Y38
Sm39
M3þ ionic radius
M(1)ꢀS(1)
0.870
1.019
1.079
2.7114(4)
2.7335(4)
2.202, 2.220
66.778(14)
113.22(1)
130.1
2.8931(6)
2.9031(6)
2.370, 2.402
61.59(2)
118.41(2)
128.5
2.9341(6)
2.9388(6)
2.429, 2.464
61.99(2)
118.01(2)
128.6
M(1)ꢀS(1)0
M(1)ꢀCnta
S(1)ꢀM(1)ꢀS(1)0
M(1)ꢀS(1)ꢀM(1)0
Cnt1ꢀM(1)ꢀCnt2
Figure 3. ORTEP of (C5Me4H)2Sc(SPh)(THF), 5, drawn at the 50%
probability level. Hydrogen atoms are omitted for clarity. (C5Me4H)2-
Sc(SePh)(THF), 6, is isomorphous and (C5Me4H)2Sc(TePh)(THF),
7, is similar but has two independent molecules in the unit cell (see
Supporting Information).
a Cnt = centroid of the cyclopentadienyl ring.
solvate-free bridged dimer, (b) a terminal Lewis base adduct, and
(c) a complex with a chelating Lewis base. In each case the metal
is eight coordinate, but Table 5 shows that these variations have
a significant effect on ScꢀS bond distances. The (ring
centroid)ꢀScꢀ(ring centroid) angles (2, 130.1°; 5, 133.5°; 8,
134.6°) suggest that 2 is the most crowded and 5 and 8 are
similar. This is consistent with the fact that 2 has the longest
ScꢀS distances. However, this is not shown by the Scꢀ(ring
centroid) distances, which overlap for 2 and 5. Although the
chelating Lewis base adduct 8 has the smallest Scꢀ(ring cen-
troid) distances, the THF adduct 5 has the shortest ScꢀS bond.
However, the ScꢀC distance in 8 could also be effected by a
contribution from a thioketone amido resonance form.43 These
data suggest that distances and angles are a result of a compli-
cated interplay of steric and electronic effects even in this similar
series of complexes. Crystal packing effects may also be impor-
tant, but are even more difficult to evaluate.
Figure 4. ORTEP of (C5Me4H)2Sc(Spy-κ2-S,N), 8, drawn at the 50%
Reactivity of (η5-C5Me4H)2Sc(η1-C5Me4H), 9, with PhEEPh
(E = S, Se, Te). (η5-C5Me4H)2Sc(η1-C5Me4H), 9, reacts with
PhEEPh reagents in a manner similar to the (C5Me4H)2Sc(η3-
C3H5) reactions described above. Reactions in toluene generate
the same scandium metallocenes obtained from 1, namely,
[(C5Me4H)2Sc(EPh)]x (E = S, 2; Se, 3; Te, 4), and in this case
(C5Me4H)EPh is observed as the byproduct, eq 5. No evidence
for (C5Me4H)2, the expected byproduct of sterically induced
reduction, was observed. In the reaction of 9 with PhSSPh, a
longer reaction time is required (5 d) for the reaction to go to
completion when compared to 1 (24 h).
probability level. Hydrogen atoms are omitted for clarity.
(pyridine)4Yb(SePh)2 and (pyridine)5Yb(TePh)2, the higher
coordination number for the tellurium complex is attributed to
longer LnꢀE bonds that place the phenyl groups further from
the lanthanide.41 This secondary coordination sphere argument
could also explain the structures of 2ꢀ4. In addition, (SePh)ꢀ
and (TePh)ꢀ are not as effective at binding as (SPh)ꢀ and would
be expected to form less favorable bridging interactions. The
structures of (C5Me4H)2Sc(EPh)(THF), 5ꢀ7, described
below demonstrate that a (SePh)ꢀ or (TePh)ꢀ unit alone does
not fully saturate the coordination sphere of scandium in
[(C5Me4H)2Sc]þ. The closest related structure is the penta-
methylcyclopentadienyl complex (C5Me5)2Sc(TeCH2C6H5),
which also crystallizes as a monomer.42 Due to disordered
toluene solvent in isomorphous complexes 3 and 4, a detailed
metrical analysis is not presented.
(C5Me4H)2Sc(EPh)(THF), 5ꢀ7. Complexes 5ꢀ7 are closely
related to the previously published (C5Me5)2Sm(EPh)(THF)
series.39 For example, bond distances and angles involving the
metal remain the same within error limits when the differences in
ionic radii40 are considered, and the MꢀE bond distances
increase in a periodic order from S to Se to Te, Table 4. Once
again, the smaller (C5Me4H)ꢀ ligand with the small scandium
gives structures similar to (C5Me5)ꢀ complexes of the
lanthanides.
’ DISCUSSION
The diphenyldichalcogenides, PhEEPh, readily participate in
reactions with (C5Me4H)2Sc(η3-C3H5), which can be explained
as σ bond metatheses. Scheme 2 shows a four-center intermedi-
ate that could be present for these reactions based on previous
studies of σ bond metathesis.18,20ꢀ22 In each of the reactions with
the allyl complex (C5Me4H)2Sc(η3-C3H5), 1, both in toluene
and in toluene/THF, the allyl phenyl chalcogenide byproduct,
(C3H5)EPh, expected from σ bond metathesis was isolated. In
each of these reactions, allyl complex 1 is acting as an η1-alkyl
(C5Me4H)2Sc(Spy-K2-S,N), 8. The structures of complexes 2,
5, and 8 present an interesting opportunity to compare metallo-
cene bonding with an X-type ligand, SPh in this case, in (a) a
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Table 4. Selected Bond Distances (Å) and Angles (deg) for (C5Me4H)2Sc(SPh)(THF), 5, (C5Me4H)2Sc(SePh)(THF),
6, (C5Me4H)2Sc(TePh)(THF), 7, (C5Me5)2Sm(SPh)(THF), 10, (C5Me5)2Sm(SePh)(THF), 11, and
(C5Me5)2Sm(TePh)(THF), 12
E, complex
S, 5
Se, 6
Te, 7a
S, 1039
Se, 1139
Te, 1239
M(1)ꢀO(1)
2.2425(9)
2.5222(4)
2.244, 2.217
1.769(1)
2.240(1)
2.241(1)
2.445(3)
2.443(3)
2.449(2)
M(1)ꢀE(1)
2.6836(3)
2.234, 2.217
1.916(1)
2.9393(3)
2.230, 2.213
2.129(2)
2.761(1)
2.8837(6)
2.448, 2.445
3.1279(3)
2.448, 2.445
M(1)ꢀCntb
2.442, 2.452
E(1)ꢀC(19)c
E(1)ꢀC(21)c
1.759(5)
133.7
1.913(4)
134.1
2.127(2)
135.2
Cnt1ꢀM(1)ꢀCnt2
C(19)ꢀE(1)ꢀM(1)
C(21)ꢀE(1)ꢀM(1)
O(1)ꢀM(1)ꢀE(1)
133.5
134.1
134.2
119.93(4)
117.72(4)
112.54(4)
120.8(2)
89.72(9)
118.5(1)
89.35(8)
112.49(6)
92.51(4)
92.16(3)
93.44(3)
94.46(3)
a There are two independent molecules of 7 in the unit cell. The distances and angles of the second independent molecule of 7 are omitted for clarity.
b Cnt = centroid of the cyclopentadienyl ring. c Ipso carbon atom of the phenyl ring.
’ CONCLUSION
Table 5. Selected Bond Distances (Å) and Angles (deg) for
[(C5Me4H)2Sc(SPh)]2, 2, (C5Me4H)2Sc(SPh)(THF), 5, and
(C5Me4H)2Sc(Spy-κ2-S,N), 8
The allyl complex (C5Me4H)2Sc(η3-C3H5), 1, demonstrates
ScꢀC bond reactivity in σ bond metathesis reactions with PhEEPh
(E = S, Se, Te) reagents. Reactions occur in good yield in both
toluene and toluene/THF to form (C3H5)EPh and the
[(C5Me4H)2Sc(EPh)]x and (C5Me4H)2Sc(EPh)(THF) com-
plexes, respectively. The bis(tetramethylcyclopentadienyl) scan-
dium reaction products show structural similarity to pentamethyl-
cyclopentadienyl yttrium and lanthanide metallocenes and demon-
strate a correlation in structure between Sc3þ with (C5Me4H)ꢀ
ligands and the larger rare earths with (C5Me5)ꢀ ligands. The
chelated Lewis base complex (C5Me4H)2Sc(Spy-κ2-S,N) forms
similarly from pySSpy and allows structural comparisons with
[(C5Me4H)2Sc(SPh)]2 and (C5Me4H)2Sc(SPh)(THF) that
show the flexibility of metallocene coordination environments with
varying Lewis bases. The tris(polyalkylcyclopentadienyl) complex,
(η5-C5Me4H)2Sc(η1-C5Me4H), also reacts with PhEEPh reagents
by σ bond metathesis, indicating that the η1-structure found in the
solid state translates into clean σ bond metathesis reactivity.
2
5
8
Sc(1)ꢀCnta
2.220, 2.202
2.7114(4)
2.7335(4)
2.244, 2.217
2.5222(4)
2.179, 2.181
2.6158(4)
Sc(1)ꢀS(1)
Sc(1)ꢀS(1)0
Sc(1)ꢀN(1)
2.249(1)
2.828(1)
134.6
Sc(1)ꢀC(19)b
Cnt1ꢀSc(1)ꢀCnt2
CntꢀSc(1)ꢀS(1)
CntꢀSc(1)ꢀS(1)0
CntꢀSc(1)ꢀO(1)
CntꢀSc(1)ꢀN(1)
130.1
133.5
111.9, 109.9
112.6, 108.0
100.7, 110.7
109.3, 110.2
104.8, 107.2
108.3, 107.9
a Cnt = centroid of the cyclopentadienyl ring. b Ipso carbon atom of the
phenyl ring.
Scheme 2. Proposed Four-Center Intermediate for the
Reactions of (C5Me4H)2Sc(η3-C3H5), 1, with PhEEPh
’ ASSOCIATED CONTENT
S
Supporting Information. X-ray data collection, structure
b
solution, and refinement (PDF) and X-ray diffraction details of
compounds 2ꢀ8 (CIF, CCDC Nos. 814911ꢀ814917). This ma-
terial is available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*Fax: 949-824-2210. E-mail: wevans@uci.edu.
ligand. Hence, the diphenyldichalcogenide reaction is another
example of accessing ScꢀC bond reactivity via allyl ligands in rare
earth complexes.27ꢀ32
Examination of the reactions of PhEEPh with (η5-
C5Me4H)2Sc(η1-C5Me4H), 9, gave the same organometallic
products, [(C5Me4H)2Sc(EPh)]x, as observed with 1 along
with the σ bond metathesis byproduct, (C5Me4H)EPh.
Hence, 9 reacts like an η1-alkyl complex, and the η1-structure
delivers pseudoalkyl reactivity. This is quite reasonable, but it
had not previously been demonstrated with a tris(poly-
alkylcyclopentadienyl) complex that had an η1-cyclopenta-
dienyl structure characterized by X-ray crystallography.
’ ACKNOWLEDGMENT
We thank the U.S. National Science Foundation for support of
this research and Professor Gerd Meyer, the University of Cologne,
and the Fonds der Chemischen Industrie for support for S.D.
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