Coupling of alkynes mediated by [RuCp(PPh2NHPh)(CH3CN)2]+: Formation of η4-butadiene amido complexes through migration and N-H activation of the PPh2NHPh ligand

Article abstract of DOI:10.1021/om020990s

This is a continuation of our work on the reactions of [RuCp(PR₃)(CH₃CN)₂]PF₆ with terminal alkynes and diynes. Here now we use, instead of PR₃, the phosphino-amine ligand PPh₂NHPh. The reaction pattern is found to be similar except that the N-H bond of the phosphine ligand is activated and not a C-H bond as before. Thus the reaction of [RuCp(PPh₂NHPh)(CH₃CN)₂]PF₆ with HC≡CR (R = Ph, n-Bu, CH₂Ph), 1,6-heptadiyne, and 1,7-octadiyne results in the formation of the η⁴-butadiene amido complexes [RuCp(η⁴-C₄H₃(R)₂ PPh_2-κ1-(N)-NPh)]PF₆, [RuCp(η⁴-C₄H₃(CH₂)₃- PPh_2-κ1-(N)-NPh)]PF₆, and [RuCp(η⁴-C₄H₃(CH₂)₄- PPh_2-κ1-(N)-NPh)]PF₆ in good yields.

Full text of DOI:10.1021/om020990s

Organometallics 2003, 22, 1771-1774
1771
Notes
Cou p lin g of Alk yn es Med ia ted by
[Ru Cp (P P h 2NHP h )(CH3CN)2]+: F or m a tion of
η4-Bu ta d ien e Am id o Com p lexes th r ou gh Migr a tion a n d
N-H Activa tion of th e P P h 2NHP h Liga n d
Sonja Pavlik,† Kurt Mereiter,‡ Roland Schmid,† and Karl Kirchner*,†,§
Institute of Applied Synthetic Chemistry and Institute of Chemical Technologies and Analytics,
Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria
Received December 9, 2002
Summary: This is a continuation of our work on the
reactions of [RuCp(PR3)(CH3CN)2]PF6 with terminal
alkynes and diynes. Here now we use, instead of PR3,
the phosphino-amine ligand PPh2NHPh. The reaction
pattern is found to be similar except that the N-H bond
of the phosphine ligand is activated and not a C-H bond
as before. Thus the reaction of [RuCp(PPh2NHPh)(CH3-
CN)2]PF6 with HCtCR (R ) Ph, n-Bu, CH2Ph), 1,6-
heptadiyne, and 1,7-octadiyne results in the formation
of the η4-butadiene amido complexes [RuCp(η4-C4H3(R)2-
PPh2-κ1-(N)-NPh)]PF6, [RuCp(η4-C4H3(CH2)3-PPh2-κ1-
(N)-NPh)]PF6, and [RuCp(η4-C4H3(CH2)4-PPh2-κ1-(N)-
NPh)]PF6 in good yields.
CN)2]PF6 (1) is reacted with terminal alkynes and
diynes. Specifically, will migration appear at the P or
the N site? As another question, will there be N-H bond
or C-H bond activation? These issues are addressed in
the present contribution.
Resu lts a n d Discu ssion
The starting complex 1 was obtained in 92% isolated
yield by reacting RuCp(CH3CN)3]PF6 with 1 equiv of
PPh2NHPh at room temperature. It is stable to air in
the solid state but decomposes slowly in solutions
exposed to air. The 1H NMR spectrum bears no unusual
features. The Cp ligand gives a singlet at 4.49 ppm. The
NH proton of the PPh2NHPh ligand gives rise to a
doublet at 6.43 ppm (2J HP ) 8.37 Hz). In the 31P{1H}
NMR spectrum the phosphino-amine ligand shows a
singlet at 81.2 ppm.
In tr od u ction
The labile complex [RuCp(PR3)(CH3CN)2]PF6 (R )
Me, Ph, Cy, etc.) is a useful starting material for a
variety of transformations since it behaves as synthetic
equivalent for the 14-electron fragment [RuCp(PR3)]+.1
For instance, it reacts with many terminal alkynes to
give ruthenium allyl carbenes.2 These in turn appear
as masked coordinatively unsaturated complexes that
react readily with the donor ligands PR3 and P(OR)3 to
give η3-butadienyl complexes.3 Furthermore, the ruthe-
nium allyl carbenes are prone to convert into η4-
butadiene complexes according to Scheme 1.4 The
overall transformation is intriguing because of the
involvement of phosphine migration and C-H bond
activation in the phosphine substituent.
Treatment of 1 with HCtCR (R ) Ph, n-Bu, CH2Ph),
1,6-heptadiyne, and 1,7-octadiyne results in the forma-
tion of the η4-butadiene amido complexes [RuCp(η4-
C4H3(R)2-PPh2-κ1-(N)-NPh)]PF6 (2a -c), [RuCp(η4-C4H3-
(CH2)3-PPh2-κ1-(N)-NPh)]PF6 (2d ), and [RuCp(η4-C4H3-
(CH2)4-PPh2-κ1-(N)-NPh)]PF6 (2e) in 43-88% isolated
yields (Schemes 2 and 3). These compounds, which are
air-stable both in solution and in the solid state, were
1
characterized by H, 13C{1H}, and 31P{1H} NMR spec-
troscopy as well as elemental analysis. The 1H NMR
spectroscopic data for 2a include characteristic reso-
3
nances at 7.26 (d, J HH ) 10.9 Hz, H3), 4.81 (d, 1H,
In this respect it was deemed worthwhile to switch
over to the phosphino-amine ligand PPh2NHPh instead
of PR3. Our intention was to see in what ways the course
of reaction is changed when [RuCp(PPh2NHPh)(CH3-
3
2J HP ) 15.8, H1), and 4.47 (d, 1H, J HH ) 10.9 Hz, H4)
assignable to the two terminal and the internal diene
protons of the coordinated η4-diene unit. In the 13C{1H}
NMR spectrum the characteristic resonance of the
coordinated sp2 carbon atoms C1, C2, C3, and C4 of the
† Institute of Applied Synthetic Chemistry.
1
‡ Institute of Chemical Technologies and Analytics.
§ E-mail: kkirch@mail.zserv.tuwien.ac.at.
butadiene moiety exhibit resonances at 29.1 (d, J CP
)
110.0 Hz), 114.2, 90.6, and 81.7 ppm, respectively. In
the 31P{1H} NMR spectrum the phosphino-amine ligand
exhibits a singlet at 46.2 ppm. Concurrent NMR spectra
are observed for 2b-e.
(1) Ru¨ba, E.; Simanko, W.; Mauthner, K.; Soldouzi, K. M.; Slugovc,
C.; Mereiter, K.; Schmid, R.; Kirchner, K. Organometallics 1999, 18,
3843.
(2) Ru¨ba, E.; Mereiter, K.; Sapunov, V. N.; Schmid, R.; Kirchner,
K.; Schottenberger, H.; Calhorda, M. J .; Veiros, L. F. Eur. J . Chem.
2002, 8, 3948.
(3) Crocker, M.; Green, M.; Nagle, K. R.; Orpen, A. G.; Neumann,
H. P.; Morton, C. E.; Schaverin, C. J . Organometallics 1990, 9, 1422.
(4) Ru¨ba, E.; Mereiter, K.; Schmid, R.; Kirchner, K.; Bustelo, E.;
Puerta, M. C.; Valerga, P. Organometallics 2002, 21, 2912.
The solid state structures of 2b and 2d were deter-
mined by single-crystal X-ray diffraction. ORTEP dia-
grams are depicted in Figures 1 and 2, with important
bond distances reported in the captions. The overall
10.1021/om020990s CCC: $25.00 © 2003 American Chemical Society
Publication on Web 03/11/2003

1772 Organometallics, Vol. 22, No. 8, 2003
Notes
Sch em e 1
Sch em e 2
F igu r e 1. Structural view of [RuCp(η4-C4H3(n-Bu)2-PPh2-
-
κ1-(N)-NPh)]PF6 (2b) showing 50% thermal ellipsoids (PF6
omitted for clarity). Selected bond lengths (Å) and angles
(deg): Ru-C(1-5)av 2.194(3), Ru-C(24) 2.229(3), Ru-C(25)
2.225(3), Ru-C(30) 2.181(3), Ru-C(31) 2.237(3), Ru-N(1)
2.173(2), N(1)-P(1) 1.599(2), C(24)-C(25) 1.416(4), C(25)-
C(30) 1.427(4), C(30)-C(31) 1.406 (4), N(1)-Ru-C(24) 71.5-
(1).
Sch em e 3
structures of 2a and 2d are very similar and can be
described as a three-legged piano stool conformation
with the N atom of the PPh2NHPh group and the two
CdC bonds of the butadiene moiety as the legs.
In 2b the butadiene C-C bonds C(24)-C(25), C(25)-
C(30), and C(30)-C(31) reveal slightly alternating bond
distances, i.e., a short-long-short pattern (1.416(4),
1.427(4), and 1.406(6) Å). Similar behavior is encoun-
tered in 2d with C(24)-C(25), C(25)-C(29), and C(29)-
C(30) being 1.426(5), 1.436(6), and 1.408(6) Å, respec-
tively. The C1-4 chain in either compound is nearly
planar, with a torsion angle of -4.4(5)°. All Ru-C
distances are rather uniform, ranging from 2.181 to
2.237 Å. The Ru-N bonds in 2b and 2d are 2.173(2)
and 2.145(3) Å, respectively, typical of a Ru-N amido
single bond in Ru(II) complexes. For comparison, the
Ru-amido nitrogen bond distances of RuTp(CO)(PPh3)-
(NHPh),5 cis-Ru(PMe3)4(H)(NHPh),6 and Ru(η6-C6Me6)-
(Ph)(PMe3)(NHPh)7 are 2.076(3), 2.160(4), and 2.121(3)
Å, respectively. The N-Ru-C angles in 2b and 2d are
F igu r e 2. Structural view of [RuCp(η4-C4H3(CH2)3-PPh2-
-
κ1-(N)-NPh)]PF6 (2d ) showing 50% thermal ellipsoids (PF6
omitted for clarity). Only one of the two crystallographically
independent complexes is shown. Selected bond lengths (Å)
and angles (deg): Ru(1)-C(1-5)av 2.210(4), Ru(1)-C(24)
2.227(3), Ru(1)-C(25) 2.229(3), Ru(1)-C(29) 2.212(4), Ru-
(1)-C(30) 2.217(4), Ru(1)-N(1) 2.145(3), N(1)-P(1) 1.605-
(3), C(24)-C(25) 1.426(5), C(25)-C(29) 1.436(6), C(29)-
C(30) 1.408 (6), N(1)-Ru(1)-C(24) 71.9(1).
71.5(1)° and 71.9(1)°, respectively. The four-membered
Ru-N-P-C ring system is essentially planar, with
torsion angles of -3.8(1)° and -3.4(1)°.
For the present conversions, unfortunately, no inter-
mediate products could be detected spectroscopically.
However, it is plausible to speculate that the formation
(5) J ayaprakash, K. N.; Gunnoe, T. B.; Boyle, P. D. Inorg. Chem.
2001, 40, 6481.
(6) Hartwig, J . F.; Andersen, R. A.; Bergman, R. G. Organometallics
1991, 10, 1875.
(7) Boncella, J . M.; Eve, T. M.; Rickman, B.; Abboud, K. A.
Polyhedron 1998, 17, 725.

Notes
Organometallics, Vol. 22, No. 8, 2003 1773
C4), 29.1 (d, 1J CP ) 110.0 Hz, 1C, C 1). 31P{1H} NMR (δ, acetone-
d6, 20 °C): 46.2 (PPh2), -144.1 (1J FP ) 707.2 Hz, PF6).
of the η4-butadiene amido complexes proceeds via a
metallacylopentatriene and an allyl carbene species as
depicted in Scheme 2. Thus, there is migration of the
κ1(P)-coordinated PPh2NHPh ligand analogously to the
η3-allyl carbene complex already described.2c In contrast,
however, instead of a C-H bond activation step involv-
ing the phenyl substituents of the PPh2NHPh ligand,
there is facile N-H activation of the NHPh moiety. In
this way novel RuCp η4-butadiene amido complexes are
afforded. This is also noteworthy in view of the com-
paratively strained four-membered Ru-N-P-C ring
system formed, in contrast to a five-membered Ru-C-
C-P-C ring system in the case of C-H bond activa-
tion.4
[Ru Cp (η4-C4H3(n -Bu )2-P P h 2-K1-(N)-NP h )]P F 6 (2b). This
complex has been prepared analogously to 2a with 1 (150 mg,
0.224 mmol) and 1-hexyne (64.3 µL, 0.559 mmol) as the
starting materials. Yield: 74 mg (43%). Anal. Calcd for
C
35H41F6NP2Ru: C, 55.85; H, 5.49; N, 1.86. Found: C, 55.76;
Exp er im en ta l Section
H, 5.44; N, 1.90. 1H NMR (δ, CD2Cl2 20 °C): 7.96-7.27 (m,
10H, Ph), 7.24-7.04 (m, 2H, NPh), 6.93-6.62 (m, 3H, NPh),
Gen er a l In for m a tion . All manipulations were performed
under an inert atmosphere of argon by using Schlenk tech-
niques. All chemicals were standard reagent grade and used
without further purification. The solvents were purified ac-
cording to standard procedures.8 The deuterated solvents were
purchased from Aldrich and dried over 4 Å molecular sieves.
[RuCp(CH3CN)3]PF6 and PPh2NHPh have been prepared
according to the literature.9,10 1H, 13C{1H}, and 31P{1H} NMR
spectra were recorded on a Bruker AVANCE-250 spectrometer
and were referenced to SiMe4 and H3PO4 (85%), respectively.
1H and 13C{1H} NMR signal assignments were confirmed by
1H-COSY, 135-DEPT, and HSQC(1H-13C) experiments.
[Ru Cp (P P h 2NHP h )(CH3CN)2]P F 6 (1). To a solution of
[RuCp(CH3CN)3]PF6 (300 mg, 0.691 mmol) in CH2Cl2 (5 mL)
was added PPh2NHPh (211 mg, 0.760 mmol), and the mixture
was stirred for 2 h at room temperature. After removal of the
solvent, a yellow powder was obtained, which was collected
on a glass frit, washed with Et2O (3 × 10 mL), and dried under
vacuum. Yield: 426 mg (92%). Anal. Calcd for C27H27F6N3P2-
Ru: C, 48.36; H, 4.06; N, 6.27. Found: C, 48.39; H, 4.02; N,
6.31. 1H NMR (δ, acetone-d6, 20 °C): 7.84-7.35 (m, 10H, Ph),
7.23-7.00 (m, 2H, NHPh), 6.95-6.73 (m, 3H, NHPh), 6.43 (d,
7.97 (d, J HH ) 10.7 Hz, H3), 5.30 (s, 5H, Cp), 4.01 (d, J HP
)
3
2
15.3 Hz, 1H, H1), 3.43 (m, 1H, H4), 2.71-2.30 (m, 2H), 2.26-
2.04 (m, 2H), 2.02-1.76 (m, 2H), 1.68-1.38 (m, 4H), 1.36-
3
3
1.12 (m, 2H), 1.03 (t, J HH ) 7.1 Hz, 3H, CH3), 0.85 (t, J HH
)
7 Hz, 3H, CH3). 13C{1H} NMR (δ, CD2Cl2, 20 °C): 145.1 (s,
1C, N-Ph1), 134.6 (d, 4J CP ) 2.8 Hz, 1C, Ph4), 134.2 (d, 4J CP
)
2.8 Hz, 1C, Ph4′), 131.2 (d, 2J CP ) 11.0 Hz, 2C, Ph2,6), 131.0 (d,
2J CP ) 11.3 Hz, 2C, Ph2,6′), 130.1 (d, 3J CP ) 12.3 Hz, 2C, Ph3,5),
129.3 (d, J CP ) 12.0 Hz, 2C, Ph3,5′), 129.3 (d, J CP ) 50.0 Hz,
3
1
1C, Ph1), 129.0 (s, 2C, NPh3,5), 127.9 (d, J CP ) 52.4 Hz, 1C,
1
Ph1′), 121.7 (d, J CP ) 12.3 Hz, 1C, NPh4), 120.3 (s, 2C, N-Ph2,6),
116.2 (s, 1C, C2), 94.0 (s, 1C, C3), 85.3 (s, 5C, Cp), 83.8 (s, 1C,
C4), 43.0 (d, J CP ) 9 Hz, 1C, CH2), 37.4 (s, 1C, CH2), 35.5 (s,
1C, CH2), 34.1 (s, 1C, CH2), 28.4 (d, J CP ) 111.8 Hz, 1C, C1),
1
22.4 (s, 1C, CH2), 21.9 (s, 1C, CH2), 13.6 (s, 1C, CH3), 13.5 (s,
1C, CH3). 31P{1H} NMR (δ, acetone-d6, 20 °C): 42.6 (PPh2),
-144.1 (1J FP ) 708.4 Hz, PF6).
[Ru Cp(η4-C4H3(CH2P h )2-P P h 2-K1-(N)-NP h )]P F6 (2c). This
complex has been prepared analogously to 2a with 1 (160 mg,
0.239 mmol) and benzylacetylene (74.3 µL, 0.598 mmol) as the
starting materials. Yield: 108 mg (55%). Anal. Calcd for
C
41H37F6NP2Ru: C, 60.00; H, 4.54; N, 1.71. Found: C, 60.08;
2J HP ) 8.37 Hz, 1H, NHPh), 4.49 (s, 5H, Cp), 2.28 (d, J HP
)
H, 4.47; N, 1.66. 1H NMR (δ, CD2Cl2 20 °C): 8.12-6.55 (m,
1.26 Hz, 6H, CH3CN). 13C{1H} NMR (δ, acetone-d6, 20 °C):
25H, Ph, NPh), 6.21 (d, J HH ) 9.7 Hz, 1H, H3), 5.44 (s, 5H,
3
143.7 (d, J CP ) 3.2 Hz, 1C, NPh1), 135.7 (d, J CP ) 46.2 Hz,
1
Cp), 4.25 (d, J HP ) 14.0 Hz, 1H, H1), 3.91-3.43 (m, 5H, CH2,
2
2
4
2C, Ph1), 131.6 (d, J CP ) 12 Hz, 4C, Ph2,6), 130.2 (d, J CP
)
H4). 13C{1H} NMR (δ, CD2Cl2, 20 °C): 145.1 (s, 1C, N-Ph1),
140.0-126.6 (26C, Ph, NPh3,5), 121.7 (d, J CP ) 13.2 Hz, 1C,
NPh4), 120.4 (s, 2C, NPh2,6), 114.9 (s, 1C, C2), 94.1 (s, 1C, C3),
85.7 (s, 5C, Cp), 83.0 (s, 1C, C4), 48.0 (d, J CP ) 9.5 Hz, 1C,
2.3 Hz, 2C, Ph4), 128.4 (2C, N-Ph3,5), 128.4 (d, J CP ) 10.1
Hz, 4C, Ph3,5), 127.9 (s, 2C, CH3CN), 120.2 (d, J CP ) 1.2 Hz,
3
1C, NPh ), 118.9 (dd, J CP ) J CP ) 6.0 Hz, 2C, NPh2,6), 77.2 (d,
4
J CP ) 2.3 Hz, 5C, Cp), 2.6 (s, 2C, CH3CN). 31P{1H} NMR (δ,
acetone-d6, 20 °C): 81.2 (PPh2), -144.1 (1J FP ) 709.6 Hz, PF6).
[Ru Cp (η4-C4H3(P h )2-P P h 2-K1-(N)-NP h )]P F 6 (2a ). To a
solution of 1 (160 mg, 0.239 mmol) in CH2Cl2 (10 mL) was
added 2.5 equiv of HCtCPh (65.5 µL, 0.598 mmol), and the
mixture was stirred for 2 h at room temperature. After removal
of the solvent under reduced pressure, a dark red solid was
obtained, which was washed with Et2O (5 mL) and dried under
vacuum. The crude product was purified by column chroma-
tography (neutral Al2O3/CH3CN). The red band was collected.
Yield: 116 mg (61%). Anal. Calcd for C39H33F6NP2Ru: C, 59.09;
CH2), 42.9 (s, 1C, CH2), 28.3 (d, J CP ) 112.5 Hz, 1C, C1). 31P-
1
{1H} NMR (δ, CD2Cl2, 20 °C): 44.2 (PPh2), -144.6 (1J FP
)
701.9 Hz, PF6).
[Ru Cp (η4-C4H3(CH2)3-P P h 2-K1-(N)-NP h )]P F 6 (2d ). This
complex has been prepared analogously to 2a with 1 (300 mg,
0.447 mmol) and 1,6-heptadiyne (61.5 µL, 0.537 mmol) as the
starting materials. Yield: 268 mg (88%). Anal. Calcd for
C
30H29F6NP2Ru: C, 52.95; H, 4.29; N, 2.06. Found: C, 52.99;
H, 4.32; N, 1.97. 1H NMR (δ, acetone-d6, 20 °C): 8.07-7.42
(m, 10H, Ph), 7.12-7.01 (m, 2H, NPh), 6.85-6.69 (m, 3H,
NPh), 5.53 (s, 5H, Cp), 5.42 (d, J HH ) 2.8 Hz, 1H, H4), 4.60
2
1
H, 4.20; N, 1.77. Found: C, 59.15; H, 4.16; N, 1.83. H NMR
(d, J HP ) 16.4 Hz, 1H, H1), 3.67-3.45 (m, 2H, CH2), 2.65-
2
(δ, acetone-d6, 20 °C): 8.48-6.51 (m, 25 H, Ph, NPh), 7.26 (d,
2.45 (m, 2H, CH2), 2.31 (d, J HH ) 2.8 Hz, 1H, H4′), 1.41-1.15
2
3J HH ) 10.9 Hz, H3), 5.48 (s, 5H, Cp), 4.81 (d, J HP ) 15.8 Hz,
2
(m, 2H, CH2). 13C{1H} NMR (δ, CD2Cl2, 20 °C): 144.1 (s, 1C,
H1), 4.47 (d, 3J HH ) 10.9 Hz, H4). 13C{1H} NMR (δ, CD2Cl2, 20
°C):144.2 (s, 1C, N-Ph1), 140.1-126.8 (26C, Ph, N-Ph3,5),
122.2 (d, J CP ) 11.3 Hz, 1C, N-Ph4), 120.9 (s, 2C, N-Ph2,6),
114.2 (s, 1C, C2), 90.6 (s, 1C, C3), 87.7 (s, 5C, Cp), 81.7 (s, 1C,
NPh 1), 134.6 (d, J CP ) 2.9 Hz, 1C, Ph4), 134.3 (d, J CP ) 2.9
4
4
Hz, 1C, Ph4′), 131.5 (d, J CP ) 10.8 Hz, 2C, Ph2,6), 131.5 (d,
2
2J CP ) 10.8 Hz, 2C, Ph2,6′), 130.0 (d, 3J CP ) 12.4 Hz, 2C, Ph3,5),
129.3 (d, 3J CP ) 11.7 Hz, 2C, Ph3,5′), 128.9 (s, 2C, NPh3,5), 128.5
(d, 1J CP ) 70.4 Hz, 1C, Ph1), 126.8 (d, 1J CP ) 92.6 Hz, 1C, Ph1′),
121.6 (d, J CP ) 12.7 Hz, 1C, NPh4), 120.2 (d, J CP ) 2.0 Hz, 2C,
(8) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals, 3rd ed.; Pergamon: New York, 1988.
(9) Gill, T. P.; Mann, K. R. Organometallics 1982, 1, 485.
(10) Cross, R. J .; Green, T. H.; Keat, R. J . Chem. Soc., Dalton Trans.
1976, 1424.
NPh2,6), 114.4 (d, J CP ) 1.6 Hz, 1C, C2), 85.7 (s, 5C, Cp), 80.5
2
(s, 1C, C3), 52.4 (s, 1C, C4), 40.0 (d, J CP ) 8.8 Hz, 1C, CH2),
38.6 (s, 1C, CH2), 25.0 (d, J CP ) 113.5 Hz, 1C, C1), 22.1 (s,
1

1774 Organometallics, Vol. 22, No. 8, 2003
Notes
1C, CH2). 31P{1H} NMR (δ, CD2Cl2, 20 °C): 42.9 (PPh2), -144.4
(1J FP ) 719.5 Hz, PF6).
methods using the program SHELXS97.11 Structure refine-
ment on F2 was carried out with the program SHELXL97.12
All non-hydrogen atoms were refined anisotropically. Hydro-
gen atoms were inserted in idealized positions and were
refined riding with the atoms to which they were bonded.
2b: C35H41F6NP2Ru, Mr ) 752.70, monoclinic, space group
P21/n (No. 14), T ) 153(2) K, a ) 14.406(2) Å, b ) 11.217(2)
Å, c ) 21.209(3) Å, â ) 96.731(2)°, V ) 3404(1) Å3, Z ) 4,
µ ) 0.613 mm-1. Of 48 352 reflections collected (θ < 30°), 9810
were independent; Rint ) 0.037; final R values: R1 ) 0.061
(all data), wR2 ) 0.115 (all data).
2d : C30H29F6NP2Ru, Mr ) 680.55, monoclinic, space group
P21/c (No. 14), T ) 173(2) K, a ) 9.204(2) Å, b ) 20.107(4) Å,
c ) 30.886(6) Å, â ) 95.402(4)°, V ) 5691(2) Å3, Z ) 8, µ )
0.724 mm-1. Of 39 379 reflections collected (θ < 27°), 12 306
were independent; Rint ) 0.052; final R values: R1 ) 0.067
(all data), wR2 ) 0.126 (all data).
[Ru Cp (η4-C4H3(CH2)4-P P h 2-K1-(N)-NP h )]P F 6 (2e). This
complex has been prepared analogously to 2a with 1 (150 mg,
0.224 mmol) and 1,7-octadiyne (35.7 µL, 0.269 mmol) as the
starting materials. Yield: 96 mg (62%). Anal. Calcd for
C
31H31F6NP2Ru: C, 53.61; H, 4.50; N, 2.02. Found: C, 53.58;
1
H, 4.53; N, 2.11. H NMR (δ, CD3NO2, 20 °C): 7.95-7.33 (m,
10H, Ph), 7.16-6.97 (m, 2H, NPh), 6.90-6.68 (m, 3H, NPh),
5.40 (s, 5H, Cp), 5.12 (d, J HH ) 3.3 Hz, 1H, H4), 4.01 (d,
2
2J HP ) 13.3 Hz, 1H, H1), 3.37-3.15 (m, 1H, CH2), 2.74-2.23
(m, 2H, CH2), 2.05 (d, J HH ) 2.5 Hz, 1H, H4′), 1.98-1.52 (m,
2
4H, CH2), 1.32-1.14 (m, 1H, CH2). 13C{1H} NMR (δ, CD2Cl2,
20 °C): 144.5 (s, 1C, NPh1), 134.6 (d, J CP ) 2.9 Hz, 1C, Ph4),
4
134.2 (d, 4J CP ) 2.9 Hz, 1C, Ph4′), 131.3 (d, 2J CP ) 11.1 Hz, 2C,
Ph2,6), 131.3 (d, J CP ) 11.4 Hz, 2C, Ph2,6′), 130.2 (d, J CP
)
2
1
70.4 Hz, 1C, Ph1), 130.0 (d, J CP ) 12.4 Hz, 2C, Ph3,5), 129.3
3
(d, J CP ) 11.7 Hz, 2C, Ph3,5′), 128.9 (s, 2C, NPh3,5), 128.6 (d,
3
1J CP ) 68.1 Hz, 1C, Ph1′), 122.3 (d, J CP ) 11.4 Hz, 1C, NPh4),
Ack n ow led gm en t. Financial support by the “Fonds
zur Fo¨rderung der wissenschaftlichen Forschung” (Project
No. P14681-CHE) is gratefully acknowledged.
120.7 (s, 2C, NPh2,6), 115.0 (s, 1C, C2), 108.1 (d, J CP ) 2 Hz,
3
1C, C3), 87.5 (s, 5C, Cp), 54.5 (s, 1C, C4), 34.2 (d, J CP ) 3.9 Hz,
1
1C, CH2), 34.1 (s, 1C, CH2), 25.7 (d, J CP ) 110.5 Hz, 1C, C1),
22.1 (d, J CP ) 2.0 Hz 1C, CH2), 21.5 (s, 1C, CH2). 31P{1H} NMR
(δ, CD2Cl2, 20 °C): 48.9 (PPh2), -144.4 (1J FP ) 719.5 Hz, PF6).
X-r a y Str u ctu r e Deter m in a tion for 2b a n d 2d . Crystals
of 2b and 2d were obtained by diffusion of Et2O into CH2Cl2
solutions. X-ray data were collected on a Bruker Smart CCD
area detector diffractometer (graphite-monochromated Mo KR
radiation, λ ) 0.71073 Å, 0.3° ω-scan frames covering
complete spheres of the reciprocal space). Corrections for
Lorentz and polarization effects, for crystal decay, and for
absorption were applied. The structures were solved by direct
Su p p or tin g In for m a tion Ava ila ble: Listings of atomic
coordinates, anisotropic temperature factors, and bond lengths
and angles for 2b and 2d . This material is available free of
charge via the Internet at http://pubs.acs.org.
OM020990S
(11) Sheldrick, G. M. SHELXS97: Program for the Solution of
Crystal Structures; University of Go¨ttingen: Germany, 1997.
(12) Sheldrick, G. M. SHELXL97: Program for Crystal Structure
Refinement; University of Go¨ttingen: Germany, 1997.