Formation of novel p-functionalized ligands by insertion reactions of RNCX (R = Ph, X = O, S; R = Pri, X = O) into the Zr-P bond of [Cp°2ZrCl(PHCy)] (Cp° = η5-C5EtMe4, Cy = Cyclohexyl) and [Cp′2<

Article abstract of DOI:10.1021/om000170k

[Cp°₂ZrCl(PHCy)] (1; Cp° = η⁵-C₅EtMe₄, Cy = cyclohexyl) and [Cp′₂ZrCl{PH(TRIP)}] (2; Cp′ = η⁵-C₅MeH₄, TRIP = 2,4,6-Prⁱ₃C₆H₂

Full text of DOI:10.1021/om000170k

Organometallics 2000, 19, 2445-2449
2445
F or m a tion of Novel P -F u n ction a lized Liga n d s by
i
In ser tion Rea ction s of RNCX (R ) P h , X ) O, S; R ) P r ,
X ) O) in to th e Zr -P Bon d of [Cp ° Zr Cl(P HCy)] (Cp ° )
2
5
η -C EtMe , Cy ) Cycloh exyl) a n d [Cp ′ Zr Cl{P H(TRIP )}]
5
4
2
5
i
(
Cp ′ ) η -C MeH , TRIP ) 2,4,6-P r C H )
5
4
3
6
2
Ulrike Segerer, J oachim Sieler, and Evamarie Hey-Hawkins*
Institut f u¨ r Anorganische Chemie der Universit a¨ t, J ohannisallee 29,
D-04103 Leipzig, Germany
Received February 23, 2000
5
[
Cp°
2
ZrCl(PHCy)] (1; Cp° ) η -C
5
EtMe
4
, Cy ) cyclohexyl) and [Cp′
) readily insert RNCX (R ) Ph, X ) S, O; R ) Pr ,
ZrCl{η -XC(PHCy)NR}] (X ) S, R ) Ph (3); X ) O, R ) Ph (4); X ) O,
2
ZrCl{PH(TRIP)}] (2;
5
i
i
Cp′ ) η -C
X ) O) to give [Cp°
5
MeH
4
3 6 2
,TRIP ) 2,4,6-Pr C H
2
2
i
2
R ) Pr (5)) and [Cp′ ZrCl{η -XC{PH(TRIP)}NR}] (X ) S, R ) Ph (6); X ) O, R ) Ph (7);
2
i
X ) O, R ) Pr (8)). 3-8 were characterized spectroscopically (IR, NMR, MS), and crystal
2
structure determinations on 4-6 showed an η bonding mode (X,N) of the XC(PHR′)NR
(
R′ ) Cy, TRIP) ligands. Of the two possible coordination modes of the ligand, 4 and 5 are
obtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr-Cl
bond, while for 6-8, both isomers (endo and exo) are formed (1:8 (6), 1:30 (7) and 1:5 (8)),
whereby the exo isomer is favored. The exo isomer of 6 was structurally characterized.
In tr od u ction
sterically less demanding substituent at phosphorus
(
“large/small”).
The insertion of polar, multiply bonded systems into
Since the first report on zirconocene(IV) complexes
with terminal dialkyl- or diarylphosphanido ligands in
the Zr-P bond of the P-functionalized zirconocene
monophosphanido complexes allows the synthesis within
the coordination sphere of zirconium of novel P-func-
tionalized phosphino ligands which are either difficult
to synthesize or are inaccessible by other routes.
Thus, CS2, diazoalkanes, phenylacetylene, carbo-
1
1
983 by Baker et al., several other group 4 complexes
with such ligands have been described; however, com-
plexes of this type with P-functionalized phosphanido
ligands are still rare.2
-8
2,10,11
1
2
13
10
While zirconocene complexes with terminal P(SiMe3)2
groups are easily accessible,4,5 complexes containing
terminal primary phosphanido ligands of general for-
14,15
15
diimides,
and isonitriles are readily inserted into
the Zr-P bond of the P-functionalized zirconocene
monophosphanido complexes [Cp 2ZrCl{P(SiMe3)2}]
(Cp ) Cp, Cp′ (Cp′ ) η -C5MeH4)). Only a few insertion
reactions of the dialkyl- or diarylphosphanido complexes
[Cp*HfCl2(PBu 2)] (with CO ) and [Cp*2HfH(PPh2)]
(with CO2 ) have been reported. Up to now, insertion
reactions of CS2, PhNCS, and MeCN with [Cp°2ZrCl-
Z
Z
mula [Cp 2ZrCl(PHR)] are only obtained with certain
Z
5
combinations of substituted cyclopentadienyl ligand and
P-R substituent. Thus, PH-functionalized zirconocene
complexes were only obtained from reactions of [Cp2-
t
16
6
i 7
t 8
9
ZrCl2] with LiPH(2,4,6-R′3C6H2) (R′ ) Me, Pr , Bu ),
i.e., a sterically less demanding ligand at Zr and a bulky
substituent at phosphorus (“small/large”), or from [Cp*2-
3
17
5
(PHCy)] (1; Cp° ) η -C5EtMe4), of ketones, aldehydes,
5
MX2] and LiPHR (Cp* ) η -C5Me5; M ) Zr, X ) Cl,
and nitriles with [Cp2ZrMe(PHMes*)] (Mes* ) 2,4,6-
t
6b
R ) Cy (cyclohexyl); M ) Hf, X ) I, Cl, R ) Cy, X ) I,
Bu 3C6H2), and of acetonitrile and benzaldehyde with
9
18
R ) Ph), i.e., a bulky substituent at Zr or Hf and a
the chelate complex [Cp*2Zr(1-PH-2-CH2-4,6-Me2C6H2)]
(
9) Vaughan, G. A.; Hillhouse, G. L.; Rheingold, A. L. Organome-
(1) (a) Baker, R. T.; Krusic, P. J .; Tulip, T. H.; Calabrese, J . C.;
tallics 1989, 8, 1760.
Wreford, S. S. J . Am. Chem. Soc. 1983, 105, 6763. (b) Baker, R. T.;
Whitney, J . F.; Wreford, S. S. Organometallics 1983, 2, 1049.
(10) Hey-Hawkins, E.; Lindenberg, F. Chem. Ber. 1992, 125, 1815.
(11) (a) Appel, R.; Moors, R. Angew. Chem. 1986, 98, 570. (b) Fritz,
G.; H a¨ rer, J .; Stoll, K.; Vaahs, T. Phosphorus Sulfur Relat. Elem. 1983,
18, 65. (c) Lindenberg, F.; Sieler, J .; Hey-Hawkins, E. Phosphorus,
Sulfur Silicon Relat. Elem. 1996, 108, 279.
(12) Hey, E.; Lappert, M. F.; Atwood, J . L.; Bott, S. G. J . Chem.
Soc., Chem. Commun. 1987, 421.
(13) Hey, E.; Lappert, M. F.; Atwood, J . L.; Bott, S. G. Polyhedron
1988, 7, 2083.
(14) Hey-Hawkins, E.; Lindenberg, F. Z. Naturforsch. 1993, 48B,
951.
(2) (a) Stephan, D. W. Angew. Chem. 2000, 112, 322. (b) Segerer,
U.; Felsberg, R.; Blaurock, S.; Hadi, G. A.; Hey-Hawkins, E. Phospho-
rus, Sulfur Silicon Relat. Elem. 1999, 144-146, 477. (c) Hey-Hawkins,
E. Chem. Rev. 1994, 94, 1661.
(
(
3) Segerer, U.; Hey-Hawkins, E. Polyhedron 1997, 16, 2537.
4) Hey-Hawkins, E.; Lappert, M. F.; Atwood, J . L.; Bott, S. G. J .
Chem. Soc., Dalton Trans. 1991, 939.
5) Lindenberg, F.; Hey-Hawkins, E. J . Organomet. Chem. 1992,
35, 291.
6) (a) Hey, E.; M u¨ ller, U. Z. Naturforsch. 1989, 44B, 1538. (b) Breen,
T. L.; Stephan, D. W. Organometallics 1996, 15, 4509.
7) Hey-Hawkins, E.; Kurz, S.; Baum, G. Z. Naturforsch. 1995, 50B,
39.
8) Kurz, S.; Hey-Hawkins, E. J . Organomet. Chem. 1994, 479, 125.
(
4
(
(15) Lindenberg, F.; Sieler, J .; Hey-Hawkins, E. Polyhedron 1996,
15, 1459.
(16) Roddick, D. M.; Santarsiero, B. D.; Bercaw, J . E. J . Am. Chem.
Soc. 1985, 107, 4670.
(
2
(
(17) Segerer, U.; Hey-Hawkins, E. Organometallics 1999, 18, 2838.
1
0.1021/om000170k CCC: $19.00 © 2000 American Chemical Society
Publication on Web 05/23/2000

2
446 Organometallics, Vol. 19, No. 13, 2000
Segerer et al.
Ta ble 1. Com p a r ison of 31P NMR a n d Selected 1
H
Sch em e 1
NMR Da ta of 1-8
1
compd
13
δ(31P) (ppm)
1J PH (Hz)
ratio
δ( H)P-H (ppm)
71.7
-4.6
209.0
230.0
226.9
224.8
215.4
246.2
241.3
244.6
241.3
233.2
234.9
3.49
4.86
3.86
3.79
3.95
7
2
3
4
5
6
6
7
7
8
8
(endo)3
(endo)
(endo)
a (endo)
b (exo)
a (endo)
b (exo)
a (endo)
b (exo)
-16.1
-50.8
-52.2
-48.8
-69.6
-75.5
-99.9
-86.9
-100.2
1:8
5.00
5.03
5.29
1:30
1:5
(Scheme 1), one with the NR group adjacent to the
chloro ligand (endo isomer) and the other with the X
group adjacent to the chloro ligand (exo isomer). Com-
3
plexes 3, 4, and 5 were obtained exclusively as the endo
isomer with the NPh group adjacent to the Zr-Cl bond.
For 6-8, both isomers were formed, with the exo isomer
3
1
being favored, as shown by P NMR studies (Table 1)
and crystal structure determination. Apparently, the
bulky cyclopentadienyl ligand Cp° favors the formation
of the endo isomer, in which the steric interaction
between the Cp° ligands and the NR group is weakest,
have been reported. A systematic study of the influence
of the steric and electronic factors of Cp and R on the
course of the insertion reaction has not yet been
undertaken.
Z
We now report the insertion reactions of RNCX (R )
2
1
while the less bulky Cp′ (or Cp) ligands favor the exo
isomer, in which the Cl-NR interaction is minimized.
The N-phenylthiophosphinoamidato and N-phenyl- or
N-isopropylphosphinoamidato ligands in 4-8 are ex-
pected to show a bidentate (O,N or S,N) coordination
mode, as was observed previously for 3 (ν(CN) 1488 and
i
Ph, X ) O, S; R ) Pr , X ) O) into the Zr-P bond of
3
[
(
Cp°2ZrCl(PHCy)] (1) (large/small) and [Cp′2ZrCl{PH-
7
i
TRIP)}] (2; TRIP ) 2,4,6-Pr 3C6H2) (small/large). Pre-
liminary results of the insertion reaction of 1 with
PhNCS have been reported elsewhere.3
-
1
3
2
ν(CS) 1022 cm ), [Cp2Zr(Cl){η -SC(H)NPh}] (ν(CN)
Resu lts a n d Discu ssion
-1 21
2
14
1
(
562 cm ), [Cp′2ZrCl{η -NPhC{P(SiMe3)2}NPh}]
N,N′ coordination; ν(CN) 1485 and 1431 cm ) and [Cp2-
ZrCl{η -S2CP(SiMe3)2}] (S,S′ coordination; ν(CS) 978
and 923 cm ). For 6, the two strong absorptions at 1490
-1
Syn th esis a n d Ch a r a cter iza tion . Recently, we
observed that [Cp°2ZrCl(PHCy)] (1) undergoes insertion
2
12
-1
2
of PhNCS into the Zr-P bond, yielding [Cp°2ZrCl{η -
-
1
-1
cm (ν(CN)) and at 1013 cm (ν(CS)) were assigned
SC(PHCy)NPh}] (3). We have now extended these
investigations to the complex [Cp′2ZrCl{PH(TRIP)}] (2)
by comparison with the products of carbodiimide, CS2,
3
,12,14,21,22
i
and PhNCS insertion.
The complexes [Cp2Zr(Me){η -OC(Me)NR}] (R ) Ph,
and the isocyanates RNCO (R ) Ph, Pr ).
2
Compound 1 was previously obtained in low yield
2
3
2
1
9
20
1-naphthyl) and [Cp2Zr(Cl){η -OC(H)NR}] (R ) Ph,
(
-
24-38%) by reaction of [Cp°2ZrCl2] and LiPHCy at
2
4
3
Cy) show strong absorptions at 1600 (R ) Ph), 1655
R ) 1-naphthyl), and 1675 cm (R ) Ph, Cy), which
70 °C in THF. We have optimized the preparation
2
3
-1
24
(
by carrying out the reaction at -40 °C in 1,2-dimethoxy-
ethane (DME), which gave 1 in 77% yield.
were assigned to the ν(CN) vibrations. The RNCO
insertion products 4 and 5 exhibit strong absorptions
i
RNCX (R ) Ph, X ) S, O; R ) Pr , X ) O) readily
-
1
-1
at 1597 and 1502 cm (4) and 1600 and 1506 cm (5),
which can be assigned to ν(CN) and ν(CO) vibrations.
Molecu la r Str u ctu r es of 4-6. In 4 and 5, the
zirconium atom is coordinated by two Cp° rings, one
chloro ligand, and the O and N atoms of the N-phenyl-
inserts into the Zr-P bond of 1 and 2 to give [Cp°2ZrCl-
2
3
{
(
η -XC(PHCy)NR}] (X ) S, R ) Ph (3); X ) O, R ) Ph
i
2
4); X ) O, R ) Pr (5)) and [Cp′2ZrCl{η -XC{PH(TRIP)}-
NR}] (X ) S, R ) Ph (6); X ) O, R ) Ph (7); X ) O,
i
R ) Pr (8)) (Scheme 1). The insertion products are
(4) or N-isopropylphosphinoamidato ligand (5), thus
colorless or yellow solids (3-6) or oils (7, 8), which are
stable to air for a short period of time. Complexes 4-8
were characterized spectroscopically (IR, NMR, MS).
Crystal structure determinations carried out on 4-6
achieving a coordination number of 5 (Figures 1 and 2,
Table 2). In 6, the zirconium atom is coordinated by two
Cp′ rings, one chloro ligand, and the S and N atoms of
the N-phenylthiophosphinoamidato ligand, thus also
achieving a coordination number of 5 (Figure 3, Table
2
showed an η bonding mode (X,N) of the XC(PHR′)NR
(R′ ) Cy, TRIP) ligands (vide infra). Because of the
2
). The overall structures are comparable to those of the
chelating action of the N-phenylthiophosphinoamidato
and N-phenyl- or N-isopropylphosphinoamidato ligand,
two isomers could, in principle, be formed in each case
3
previously reported complex 3, the thioformamido
(21) Mei, W.; Shiwei, L.; Meizhi, B.; Hefu, G. J . Organomet. Chem.
1
993, 447, 227.
(
18) (a) Hou, Z.; Stephan, D. W. J . Am. Chem. Soc. 1992, 114, 10088.
b) Hou, Z.; Breen, T. L.; Stephan, D. W. Organometallics 1993, 12,
158.
(22) Weidlein, J .; M u¨ ller, U.; Dehnicke, K. Schwingungsfrequenzen
(
3
I, Hauptgruppenelemente; G. Thieme Verlag: Stuttgart, Germany,
1981.
(
(
19) Kurz, S.; Hey-Hawkins, E. Z. Kristallogr. 1993, 205, 61.
20) (a) Hey-Hawkins, E.; Kurz, S. Phosphorus, Sulfur Silicon Relat.
(23) Gambarotta, S.; Strologo, S.; Floriani, C.; Chiesi-Villa, A.;
Guastini, C. Inorg. Chem. 1985, 24, 655.
Elem. 1994, 90, 281. (b) Frenzel, C.; L o¨ nnecke, P.; Hey-Hawkins, E.
Z. Anorg. Allg. Chem., manuscript in preparation.
(24) Gambarotta, S.; Strologo, S.; Floriani, C.; Chiesi-Villa, A.;
Guastini, C. J . Am. Chem. Soc. 1985, 107, 6278.

Formation of Novel P-Functionalized Ligands
Organometallics, Vol. 19, No. 13, 2000 2447
2
F igu r e 3. Molecular structure of [Cp′
2
ZrCl{η -SC{PH-
2
(TRIP)}NPh}] (6) showing the atom-numbering scheme
employed (ORTEP, 50% probability, SHELXTL PLUS;
XP).26 Hydrogen atoms (other than P-H) are omitted for
clarity.
F igu r e 1. Molecular structure of [Cp°
2
ZrCl{η -OC(PHCy)-
NPh}] (4) showing the atom-numbering scheme employed
ORTEP, 50% probability, SHELXTL PLUS; XP).26 Hydro-
(
gen atoms (other than P-H) are omitted for clarity.
2
23
the related complex [Cp2Zr(Me){η -OC(Me)NPh}] (O,N
coordination). The guanidino ligand, the phosphino-
dithioformato ligand, and the formamido ligand are
bonded to the zirconium atom almost symmetrically in
a bidentate fashion (phosphaguanidino ligand, Zr-N )
1
4
2
.309(5), 2.348(5) Å; phosphinodithioformato ligand,
1
2
Zr-S ) 2.733(7), 2.640(8) Å; formamido ligand,
2
3
Zr-O ) 2.298(4), Zr-N ) 2.297(4) Å ), as are the
N-phenyl- (4: Zr-N ) 2.309(3) and 2.327(3) Å,
Zr-O ) 2.268(2) and 2.262(2) Å) and N-isopropylphos-
phinoamidato ligands (5: Zr-N ) 2.349(2) Å, Zr-O )
2
.273(2) Å). In 6 (Zr-N ) 2.418(2) Å, Zr-S ) 2.658(1)
Å) and the related complex [Cp2Zr(Cl){η -SC(H)NPh}]
Zr-N ) 2.408(9) Å, Zr-S ) 2.659(4) Å), the N,S
2
21
(
coordination is unsymmetrical. The Zr-N bond lengths
of 4-6 are comparable to those of the N,N′-bonded
ligand, and the Zr-S bond length of 6 is comparable to
those of the S,S′-bonded ligand. However, in all these
complexes, delocalization of the π electrons of the N2C,
NCS, and NCO fragments can be assumed, as the C-N,
C-S, and C-O bonds are shorter than expected for
single bonds, and the N and C atoms of the N2C
2
F igu r e 2. Molecular structure of [Cp°
2
ZrCl{η -OC(PHCy)-
i
NPr }] (5) showing the atom numbering scheme employed
ORTEP, 50% probability, SHELXTL PLUS; XP). Hydro-
gen atoms (other than P-H) are omitted for clarity.
2
6
(
1
4
(C-N ) 1.331(7), 1.323(7) Å), NCO (4, N-C(35) )
Ta ble 2. Selected Bon d Len gth s (Å) a n d Bon d
1.309(4) Å, O-C(35) ) 1.209(4) Å; 5, N-C(23) ) 1.299-
(4) Å, O-C(23) ) 1.299(3) Å) and NCS fragments (3,
N-C(23) ) 1.296(6) Å, S-C(23) ) 1.718(5) Å; 6,
N-C(13) ) 1.311(4) Å, S-C(13) ) 1.723(3) Å) are
3
An gles (d eg) of 3, 4, 5, a n d 6
33
4
5
6
Zr-Cl
Zr-S
Zr-O
Zr-N
S-C*
O-C*
N-C*
P-C*
P-H
2.523(1) 2.5035(9), 2.5028(9) 2.5217(7) 2.5176(9)
2.769(1) 2.658(1)
3
coordinated in a trigonal-planar fashion. As in 3, the
2.268(2), 2.262(2)
2.273(2)
chlorine atom and the ZrXCN fragments (X ) O, S) in
2.361(4) 2.309(3), 2.327(3)
1.718(5)
2.349(2) 2.418(2)
1.723(3)
4
-6 are coplanar. The P atom of the pyramidal PHR
a
group deviates from this plane by 0.070 (P1) and 0.001
Å (P2) (4), 0.149 Å (5) and 0.393 Å (6). The mean P-C
bond length of 1.86 Å is indicative of single bonds (Table
2).
1.290(4), 1.289(4)
1.299(3)
1.296(6) 1.309(4), 1.311(4)
1.842(4) 1.855(4), 1.857(3)
1.258(2) 1.30(4), 1.26(4)
1.299(4) 1.311(4)
1.882(3) 1.847(3)
0.960
1.33(3)
Of the two possible coordination modes of the ligand,
for 4 and 5 the only one observed is that in which the
NR group is adjacent to the Zr-Cl bond (endo isomer),
while the exo isomer is observed for 6.
C*-N-Zr 106.5(3) 93.2(2), 92.5(2)
S-C*-N 114.4(3)
92.0(2)
102.5(2)
113.9(2)
O-C*-N
S-Zr-N
O-Zr-N
114.2(3), 114.5(3)
115.7(2)
56.83(7)
58.8(1)
60.2(1)
56.95(9), 56.90(9)
a
C*: 3, C(23); 4/1, C(35); 4/2, C(70); 5, C(23); 6, C(13).
Exp er im en ta l Section
2
21
complex [Cp2Zr(Cl){η -SC(H)NPh}], the phosphaguani-
All experiments were carried out under purified dry argon.
Solvents were dried and freshly distilled under argon. NMR
spectra were recorded on an Avance DRX 400 spectrometer
(Bruker). NMR standards: 1H NMR (400 MHz), trace amounts
2
14
dino complex [Cp′2ZrCl{η -NPhC{P(SiMe3)2}NPh}]
N,N′ coordination), and the CS2 insertion product [Cp2-
ZrCl{η -S2CP(SiMe3)2}] (S,S′ coordination), as well as
(
2
12

2
448 Organometallics, Vol. 19, No. 13, 2000
; 13C NMR (100.6 MHz), internal
Segerer et al.
M+ - Cl), 476 (97%, M - Cp°), 423 (23%, Cp°
+
ZrCl ), 290
+
of protonated solvent, C
solvent; P NMR (162 MHz), external 85% H PO . The IR
spectra were recorded as KBr mulls on a Perkin-Elmer FT-IR
spectrometer System 2000 in the range 350-4000 cm . The
mass spectra were recorded with a Sektorfeldger a¨ t AMD 402
6
D
6
2
3
1
+
i+
3
4
(28%,
Et) ZrNC ), 200 (7%, OC(PHCy)NPr ), 149 (29%, Cp° ), 141
+
3
(17%, NCPHCy ), 134 (15%, C ), 116 (53%, PHCy ),
5 3 5
C Me ZrCl or ZrOC(PCy)NPr ), 268 (21%, (C -
+
i +
+
2
-
1
+
+
5
EtMe
91 (7%, Zr ), 83 (100%, Cy ), 43 (97%, Pr ), and fragmentation
thereof. Anal. Calcd for C32 53ClNOPZr (625.39): C, 63.7; H,
+
+
i+
(AMD Intectra GmbH; EI, 70 eV). The melting points were
H
determined in sealed capillaries under argon and are uncor-
7.8; N, 2.1. Found: C, 62.9; H, 8.4; N, 2.0.
7
3
2
rected. 2 and 3 were prepared by literature procedures.
[Cp ′ Zr Cl{η -SC{P H(TRIP )}NP h }] (6). At room temper-
2
i
PhNCS, PhNCO, and Pr NCO are commercially available and
ature 0.45 mL (3.77 mmol) of PhNCS was added to a suspen-
sion of 1.78 g (3.42 mmol) of 2 in 50 mL of pentane. The color
of the reaction mixture became lighter, and after 30 min a
colorless solid had formed. The mixture was stirred for 2 h,
during which time the solution turned yellow. The solid was
isolated by filtration, washed with pentane, and dried in vacuo.
were kept over molecular sieves prior to use.
Im p r oved Syn th esis of [Cp °
C 1.2 g (9.8 mmol) of LiPHCy in 15 mL of DME was added to
a solution of 4.5 g (9.7 mmol) of [Cp° ZrCl ] in 30 mL of DME.
2
Zr Cl(P HCy)] (1). At -40
°
2
2
The solution was kept at this temperature for 3 h, during
which time the color changed to dark red. After the mixture
was stirred at room temperature for 12 h, LiCl was filtered
off, and the mother liquor was kept at room temperature. Pure
3
1
A
6 6
P NMR spectrum of the solid (C D ) showed two signals
1
at -48.8 ppm (d, J PH ) 246.2 Hz, endo isomer, 6a ) and -69.6
ppm (d, J PH ) 241.3 Hz, exo isomer, 6b) in the ratio 1:8. The
1
1
crystallized in 77% yield. The spectroscopic data are in
mother liquor was further concentrated, and a colorless solid
was obtained. Recrystallization from toluene yielded colorless
crystals of 6b (yield 70%). Mp: 110 °C (melts and turns yellow).
The assignment of the signals in the 13C NMR spectrum of 6b
3
agreement with those reported in the literature.
2
[
Cp °
2
Zr Cl{η -OC(P HCy)NP h }] (4). At room temperature
0
2
.51 mL (4.66 mmol) of PhNCO was added to a solution of
1
13
.48 g (4.59 mmol) of 1 in 50 mL of pentane. Immediately, the
was made on the basis of a 2D NMR spectrum ( H/ C). 6a
3
1
was not obtained in pure form.
color of the solution changed from dark red to yellow. A
NMR spectrum of the reaction mixture (C
signal at -50.8 ppm (d, J PH ) 224.8 Hz). Colorless crystals
were obtained on concentrating the solution (at room temper-
ature). Yield: 81%. Mp: 142 °C. H NMR (C
6
1
P
1
CH, 3J HH ) 6.2 Hz),
CH,
Me),
D
6
) showed only one
6b. H NMR (C
6
D
6
): δ 1.18 (d, 6H, Me
CH, 3
HH ) 6.2 Hz), 1.39 (d, 6H, Me
HH ) 6.7 Hz), 2.20 (s, 3H, C Me), 2.23 (s, 3H, C
2.76 (sept, 1H, Me HH ) 6.9 Hz), 3.76 (sept, br, 2H,
CH, 3
Me
CH), 5.00 (d, 1H, P-H, 1J PH ) 238.9 Hz), 5.48 (m, 1H,
Me), 5.56 (m, 1H, C Me), 5.61 (m, 1H, C Me), 5.68
(m, 3H, C Me), 6.07 (m, 2H, C Me), 7.02 (m, 1H, Ph),
7.18-7.09 (m, Ph and 2,4,6-Pr
2
6
1
1.28 (d, 6H, Me
J
2
J
2
3
5
H
4
5 4
H
1
D
6
): δ 0.95 (t,
2
J
6
3
H, CH
.90, 1.93, and 1.96 (s, each 3H, C
Me Et), 2.01 (s, 4H, C
), 3.79 (d, 1H, P-H, J PH ) 227 Hz), 6.96-6.98
2
CH
3
, J HH ) 7.4 Hz), 0.98-1.80 (m, br, 11H, Cy), 1.89,
Me Et), 1.97 (s, 6H, C Me
Me Et), 2.48 (q, br,
2
-
C
5
H
4
5
H
4
5 4
H
5
4
5
4
Et), 2.00 (s, 2H, C
H, CH CH
m, 1H, Ph), 7.19-7.25 (m, 4H, Ph). C NMR (C
2.90 (s, C Me Et), 15.28 and 15.38 (s, C Me CH
and 21.04 (s, C Me CH CH ), 26.94 (s, C4 of Cy), 27.59 (d, C3
or C5 of Cy, J PC ) 14.5 Hz), 27.95 (d, C3 or C5 of Cy, J PC
5
4
5
4
5
H
4
5
H
4
1
i
). 13C NMR (C
4
(
1
2
3
3
C
6
H
2
i
6
2
D
6
): δ 16.26
1
3
i
D
2
6
): δ 12.55-
CH ), 21.00
(s, C
25.39 (s, Me
Me
5
H
4
Me), 24.67 (s, Me
2
i
CH of p-Pr ), 25.19 (s, Me
CH of o-Pr ),
6
i
2
CH of o-Pr ), 34.32 (s, Me
2
CH of o-Pr ), 34.46 (s,
5
4
5
4
3
i
2
CH of p-Pr ), 108.72, 110.14, 113.53, 114.22, 115.89, 116.10,
5
4
2
3
3
3
)
118.00, 118.64, and 119.63 (each s, C
C5 of 2,4,6-Pr C H
3 6 2
5
H
4
Me), 122.53 (d, C3/
, J PC ) 4.7 Hz), 124.69, 126.20, 129.72,
and 130.16 (each s, C2-C6 of Ph), 140.0 (s, C1 of Ph), 151.44
2
i
3
7
.4 Hz), 31.54 (d, C2 or C6 of Cy, J PC ) 5.9 Hz), 33.20 (d, C2
or C6 of Cy, J PC ) 5.8 Hz), 33.69 (d, C1 of Cy, 1J PC ) 23.0
2
i
2
Hz), 120.25, 120.41, 120.90, 121.04, 121.74, 122.04, 122.13, and
1
1
3 6 2
(d, C2/C6 of 2,4,6-Pr C H , J PC ) 3.9 Hz), 152.58 (s, C4 of
i 1
i
22.70 (each s, C
4
Me
4
CEt), 125.59 (s, C
4
Me
4
CEt), 126.45,
3 6 2 3 6 2
2,4,6-Pr C H ), 155.65 (d, br, C1 of 2,4,6-Pr C H , J PC ) 14.2
1
26.70, 126.83, and 126.85 (each s, C2-C6 of Ph), 146.13 (s,
Hz), 206.4 (d, NCP, J PC ) 54.6 Hz). EI MS: m/z 538 (1%, Cp′
2
-
-
1
+
C1 of Ph), 184.48 (d, NCP, J PC ) 34.4 Hz). EI MS: m/z 657
Zr(Cl)NPhC(S)PHC
6
CH
3
), 506 (3%, Cp′
2
Zr(Cl)NPhCPHC
6
+
+
+
+
+
(
4
4%, M ), 545 (0.5%, M - Ph - Cl), 508 (100%, M - Cp°),
CH
3
), 496 (0.5%, Zr(Cl){SC{PH(TRIP)}NPh} ), 370 (20%,
SC{PH(TRIP)}NPh or Cp′Zr(Cl)SC(P)NPh ), 338 (64%,
PhNCPH(TRIP) ), 317 (5%, Cp′
246 (25%, CP(TRIP) ), 235 (21%, PH(TRIP) ), 219 (4%, PC
CH ), 203 (72%, TRIP ), 191 (11%, PC
(100%, SCPNPh ), 160 (14%, PC
Pr ), 135 (50%, PHC
118 (11%, PC CH or C H Pr ), 91 (30%, Zr ), 77 (62%, Ph ),
+
+
+
+
+
23 (11%, Cp°
2
ZrCl ), 387 (9%, Cp°
2
Zr ), 359 (2%, M - 2 Cp°),
+
+
+
+
+
3
Et)
07 (5%, ZrNPhCPCy ), 291 (13%, Cp°ZrClO ), 269 (14%, (C
5
-
2
ZrClS ), 282 (9%, Cp′
2
ZrS ),
+
+
+
+
+
Zr ), 218 (4%, PhNCPHCy ), 149 (20%, Cp° ), 135 (21%,
6
H
), 166
2
-
2
+
+
+
i
+
+
Pri
Pri
+
+
C
5
EtMe
mentation thereof. Anal. Calcd for C35
C, 63.7; H, 7.8; N, 2.1. Found: C, 62.9; H, 8.4; N, 2.0.
3
), 119 (21%, PhNCO ), 103 (5%, PhNC ), and frag-
Pr
2
CH
3
6
H
H
2
2
+
i
+
H
51ClNOPZr (659.41):
6
H
2
Pr C or C
6
+
2
2
), 149
i +
+
(16%, PHC
6
H
6
2
6
H
2
CHCH
3
or PhNCS ),
+
i
+
2
+
+
2
i
[
Cp °
2
Zr Cl{η -OC(P HCy)NP r }] (5). At room temperature
3
6
2
+
i +
i
5
64 (8%, C H4 ), 43 (66%, Pr ) and fragmentation thereof
0
1
.36 mL (3.69 mmol) of Pr NCO was added to a solution of
43
(molecular ion peak is not observed). Anal. Calcd for C34H -
.99 g (3.69 mmol) of 1 in 50 mL of pentane. Immediately, the
ClNSPZr (655.39): C, 62.3; H, 6.6; N, 2.1; S, 4.9. Found: C,
color of the solution changed from dark red to yellow. The
3
1
62.3; H, 5.9; N, 2.1; S, 4.3.
solution was stirred for 24 h. A P NMR spectrum of the
reaction mixture (C ) showed only one signal at -52.2 ppm
PH ) 215.4 Hz). Colorless crystals were obtained on
2
D
6
[Cp ′
2
Zr Cl{η -OC{P H(TRIP )}NP h }] (7). At room temper-
6
1
(d,
J
ature 0.4 mL (3.66 mmol) of PhNCO was added to a suspension
of 1.56 g (3.00 mmol) of 2 in 50 mL of pentane. The solid
dissolved at once, and a clear yellow-orange solution was
obtained. The mixture was stirred for 12 h, during which time
1
concentrating the solution. Yield: 85%. Mp: 133 °C. H NMR
3
(C
6
D
6
): δ 0.94 (t, 6H, CH
br, 11H, Cy), 1.34 (d, 6H, Me
Me Et), 1.93 (s, 6H, C Me
q, br, 4H, CH , J HH ) 7.2 Hz), 3.81 (sept, br, 1H, Me
2 3
CH , J HH ) 8.1 Hz), 1.20-2.75 (m,
3
2
CH, J HH ) 6.4 Hz), 1.90 (s, 6H,
Et), 1.95 (s, 12H, C Me Et), 2.44
CH),
): δ 12.53,
Et), 15.31
), 21.04 and 21.08 (each s,
CH), 26.98 (s, C4 of Cy), 27.71
the solution turned pale yellow. A 31P NMR spectrum of the
C
(
3
1
5
4
5
4
5
4
3
1
CH
3
1
2
solution (C
6
D
6
) showed two signals at -75.5 ppm (d, J PH
)
2
13
1
.95 (d, 1H, P-H, J PH ) 215.5 Hz). C NMR (C
2.70, 12.72, 12.90, 12.97, and 13.03 (each s, C
6
D
6
244.6 Hz, 7a ) and -99.9 ppm (d, J PH ) 241.3 Hz, 7b) in the
ratio 1:30. The solvent was evaporated, and an oily yellow
residue was obtained which did not solidify. Further purifica-
5
Me
4
and 15.40 (each s, C
C
5
Me
4
CH
2
CH
3
tion of the major isomer was not achieved.
5
Me CH CH ), 25.00 (s, Me
4
2
3
2
3
1
CH, 3J HH ) 6.9 Hz),
CH,
Me),
HH ) 6.8 Hz), 3.69 (sept, br, 2H,
(
d, C3 or C5 of Cy, J PC ) 14.9 Hz), 28.20 (d, C3 or C5 of Cy,
7b. H NMR (C
6
D
6
): δ 1.14 (d, 6H, Me
2
3
2
CH, 3
J
PC ) 7.1 Hz), 30.88 (d, C2 or C6 of Cy, J PC ) 5.5 Hz), 33.45
1.21 (d, 6H, Me
HH ) 6.7 Hz), 1.85 (s, 3H, C
2
J
HH ) 6.5 Hz), 1.33 (d, 6H, Me
2
2
1
3
(d, C2 or C6 of Cy, J PC ) 5.1 Hz), 34.01 (d, C1 of Cy, J PC
)
J
5
H
4
Me), 2.12 (s, 3H, C H
5 4
3
CH, 3
2
1
4.3 Hz), 51.39 (d, Me
20.56, 120.60, 121.90, 121.97, 122.28, and 122.70 (each s, C
CEt), 126.14 and 126.44 (each s, C Me CEt), 180.72 (d,
PC ) 33.7 Hz). EI MS: m/z 625 (4%, M ), 590 (2%,
2
CH, J PC ) 10.0 Hz), 120.03, 120.34,
2.71 (sept, 1H, Me
Me
5.74, 5.83, 5.86 (each m, each 1H, C
Me), 6.96-7.07, 7.11, 7.18-7.23 (each m, 7H, Ph and 2,4,6-
2
J
1
4
-
2
CH), 5.03 (d, 1 H, P-H, J PH ) 242.7 Hz), 5.61, 5.68, 5.73,
5 4
Me), 5.96 (m, 2H, C H -
Me
NCP,
4
4
4
5
H
4
1
+
J

Formation of Novel P-Functionalized Ligands
Pri ). 13C NMR (C
Organometallics, Vol. 19, No. 13, 2000 2449
3
C
6
H
2
6
D
6
): δ 15.64 and 16.02 (each s,
Me), 24.67, 24.70, 25.57 (each s, Me CH), 34.16, 34.29,
CH), 110.45, 110.61, 113.54, 114.24,
Ta ble 3. Cr ysta l Da ta a n d Str u ctu r e Refin em en t
C
5
H
4
2
Deta ils for 4-6
and 35.41 (each s, Me
2
4
5
6
1
C
15.05, 115.29, 115.69, 115.89, 118.02, and 119.70 (each s,
Me), 122.27 (d, C3/C5 of 2,4,6-Pri
3
formula
C35H51Cl-
NOPZr
659.41
C32H53Cl-
NOPZr
625.39
C34H43Cl-
NPSZr
655.39
5
H
4
C H , J PC ) 3.8 Hz),
3 6 2
1
1
1
26.15, 126.48, 126.95, and 127.56 (each s, C2-C6 of Ph),
i
Mr
39.81 (s, C1 of Ph), 146.77 (s, br, C2/C6 of 2,4,6-Pr
3
C
6
H
2
),
temp (K)
cryst syst
space group
a (Å)
b (Å)
c (Å)
213(2)
223(2)
223(2)
i
51.89 (s, C4 of 2,4,6-Pr
3
C
6
H
2
1
), 154.77 (d, br, C1 of 2,4,6-
triclinic
P 1h (No. 2)
10.097(1)
17.825(1)
19.553(1)
104.96(1)
91.95(1)
91.37(1)
3395.8(3)
4
monoclinic
P2 /n (No. 14) P 1h (No. 2)
1
triclinic
i
Pr
3
C
6
H
2
), 185.88 (d, br, NCP, J PC ≈ 35 Hz).
2
i
[
Cp ′
2
Zr Cl{η -OC{P H(TRIP )}NP r }] (8). At room temper-
16.366(1)
11.037(1)
18.673(1)
90
106.37(1)
90
3236.3(1)
4
1.284
9.689(1)
13.260(1)
14.087(1)
70.75(1)
76.65(1)
76.74(1)
1639.1(1)
2
i
ature 0.26 mL (2.65 mmol) of Pr NCO was added to a
suspension of 1.32 g (2.54 mmol) of 2 in 50 mL of pentane.
The mixture was stirred for 10 h, during which time the
R (deg)
â (deg)
γ (deg)
3
1
solution turned orange. The P NMR spectrum of the solution
1
(C
6
D
6
) showed two signals at -86.9 ppm (d, J PH ) 233.2 Hz,
3
V (Å )
1
8
a ) and -100.2 ppm (d, J PH ) 234.9 Hz, 8b) in the ratio 1:5.
Z
The solvent was evaporated, and an oily residue was obtained.
Fcalcd (Mg m-3)
1.290
1392
1.328
684
By washing with hexane, the isomer 8b was enriched (ratio
F(000)
1328
1
:12) but did not solidify.
cryst size (mm)
0.25 × 0.25 × 0.25 × 0.20 × 0.25 × 0.25 ×
0.20 0.20 0.20
0.476 0.496 0.552
2.2-56.2
1
CH of TRIP, 3J HH
)
8
b. H NMR (C
6
D
6
): δ 1.17 (d, 6H, Me
2
abs coeff (mm-1)
2θmax (deg)
no. of rflns collected 18 695
no. of indep rflns
Rint
3
6
6
.9 Hz), 1.30 (d, 6H, Me
2
CH of TRIP, J HH ) 6.7 Hz), 1.36 (d,
CH of TRIP, J HH ) 6.6 Hz), 1.44 (d, 3H, Me CH of
CH of Pr N, J HH ) 6.4
Me), 2.07 (s, 3H, C Me), 2.75 (sept,
CH, J HH ) 6.3 Hz), 5.29
d, 1H, P-H, J PH ) 235.2 Hz), 5.55 and 5.63 (each m, each
H, C Me), 5.65 (m, 2H, C Me), 5.77, 5.80, 5.88, and 5.93
each m, each 1H, C Me), 7.14 (s, 2H, 2,4,6-Pr
NMR (C ): δ 15.67 and 16.03 (each s, C Me), 24.36, 24.48,
4.70, 24.73, 24.80, and 25.59 (each s, Me CH of TRIP and
3
3.0-54.4
24 776
6547
3.1-55.8
10 837
6771
H, Me
2
2
i
3
i
3
Pr N, J HH ) 6.3 Hz), 1.47 (d, 3H, Me
Hz), 1.84 (s, 3H, C
H, Me CH), 3.75 (sept, br, 3H, Me
2
13 495
0.0330
1135
5
H
4
5 4
H
0.0459
334
0.0288
525
3
1
(
1
(
2
2
no. of params
R1 (I > 2σ(I))
wR2 (all data)
1
0.0534
0.1125
0.444
0.0405
0.1353
0.963
0.0402
0.1101
0.495
5
H
4
5 4
H
i
13
(∆/F)
(e Å-3)
5
H
4
3
C
6
H
2
).
C
min
-
3
(
∆/F)max (e Å
)
-0.826
-0.828
-0.534
6
D
6
5 4
H
2
2
Restrictions for 6: Zr, Cl, P, N, S, and C atoms anisotropic. H
atoms were located by difference maps and refined isotropically
i
i
i
Pr -NCP), 34.21 (s, Me
2
i
CH of o-Pr ), 35.43 (s, Me
CH of Pr -NCP, J PC ) 8.7 Hz), 110.72, 112.07,
2
CH of p-Pr ),
3
5
1
1
3.00 (d, Me
2
(for 4 and 6). For 5, H atoms were refined (fixed Ueq) in
12.91, 115.03, 115.52, 115.58, and 116.08 (each s, C
5
H
4
Me),
, J PC ) 4.1 Hz), 123.60
, J PC ) 6.4 Hz), 126.41 (s, C2 or
calculated positions.
i
3
3 6 2
22.33 (d, C3 or C5 of 2,4,6-Pr C H
i
3
(d, C3 or C5 of 2,4,6-Pr
3
C
6
H
2
i
i
Ack n ow led gm en t. We gratefully acknowledge sup-
port of this work by the Deutsche Forschungsgemein-
schaft and the Fonds der Chemischen Industrie.
C6 of 2,4,6-Pr
1
3
C
6
H
2
), 127.33 (s, C2 or C6 of 2,4,6-Pr
3
i
C
6
H
2
),
i
51.92 (s, C4 of 2,4,6-Pr
3
C
6
H
2
), 154.88 (d, C1 of 2,4,6-Pr
3
C
6
H
2
,
1
1
J
PC ) 12.3 Hz), 182.31 (d, NCP, J PC ) 34.5 Hz).
Da ta Collection a n d Str u ctu r a l Refin em en t of 4-6.
Crystallographic data are given in Table 3. Data (λ(Mo KR) )
.710 73 Å) were collected with a Siemens CCD (SMART)
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 4-6. This material is
available free of charge via the Internet at http://pubs.acs.org.
0
diffractometer. All observed reflections were used for deter-
mination of the unit cell parameters. Empirical absorption
correction was carried out with SADABS. The structures
2
5
OM000170K
2
6
were solved by direct methods (SHELXTL PLUS ). Restric-
tions for 4 and 5: Zr, Cl, P, N, O, and C atoms anisotropic.
(
26) SHELXTL PLUS; Siemens Analytical X-ray Instruments,
Madison, WI, 1990: XS, Program for Crystal Structure Solution; XL,
Program for Crystal Structure Determination; XP, Interactive Molec-
ular Graphics.
(
25) Sheldrick, G. M. SADABS-a Program for Empirical Absorption
Correction; University of G o¨ ttingen, G o¨ ttingen, Germany, 1998.