Heteromultimetallic transition metal complexes based on unsymmetrical platinum(II) bis-acetylides

Article abstract of DOI:10.1021/om800232m

The synthesis of a unique series of heteromultinuclear transition metal complexes with up to seven different metal atoms is reported by using consecutive synthesis methodologies including metathesis, dehydrohalogenation, and carbon-carbon cross-coupling reactions. In these compounds the metals Ti, Fe, Ru, Os, Re, Pt, and Cu are connected via carbon-rich bridging units comprising 1,3,5-triethynylbenzene and 2,2′-bipyridyl-5-yl. These molecules have been characterized by elemental analysis, IR and NMR spectroscopy, and ESI-TOF mass spectrometry. The main structural feature of these compounds is an unsymmetrical irans-configurated platinum(II) bis-acetylide unit. The structure of 1-(FcC≡C)-3-[(^tBu ₂bpy)(CO)₃ReC≡C]-5-[trans-(Ph₃P) ₂(RcC≡C)PtC≡C]C₆H₃ (3) and 1,3-[(Ph₃P)₂(η⁵-C₅H ₅)OsC≡C]₂-5-[(CO)₃(Cl)Re(bpyC≡C)] C₆H₃ (18) (Fc = (η⁵-C₅H ₅)(η⁵-C₅H₄)Fe; Rc = (η⁵-C₅H₅)(η⁵-C ₅H₄)Ru; ^tBu₂bpy = 4,4′-di-tert-butyl-2,2′-bipyridyl; bpy = 2,2′-bipyridyl-5-yl) in the solid state is reported. Both compounds are characterized by the central 1,3,5-triethynylbenzene core, bridging the individual transition metal building blocks. These organometallic fragments show thereby typical structural properties. The appropriate metal acetylide moieties are, as expected, found in a linear arrangement with representative M-C and C≡C bond distances.

Full text of DOI:10.1021/om800232m

3534
Organometallics 2008, 27, 3534–3546
Heteromultimetallic Transition Metal Complexes Based on
Unsymmetrical Platinum(II) Bis-Acetylides
Rico Packheiser, Petra Ecorchard, Tobias Ru¨ffer, and Heinrich Lang*
Technische UniVersita¨t Chemnitz, Fakulta¨t fu¨r Naturwissenschaften, Institut fu¨r Chemie, Lehrstuhl fu¨r
Anorganische Chemie, Strasse der Nationen 62, 09111 Chemnitz, Germany
ReceiVed March 12, 2008
The synthesis of a unique series of heteromultinuclear transition metal complexes with up to seven
different metal atoms is reported by using consecutive synthesis methodologies including metathesis,
dehydrohalogenation, and carbon-carbon cross-coupling reactions. In these compounds the metals Ti,
Fe, Ru, Os, Re, Pt, and Cu are connected via carbon-rich bridging units comprising 1,3,5-triethynylbenzene
and 2,2′-bipyridyl-5-yl. These molecules have been characterized by elemental analysis, IR and NMR
spectroscopy, and ESI-TOF mass spectrometry. The main structural feature of these compounds is an
unsymmetrical trans-configurated platinum(II) bis-acetylide unit. The structure of 1-(FcCt C)-3-
[(tBu2bpy)(CO)3ReCt C]-5-[trans-(Ph3P)2(RcCt C)PtCt C]C6H3 (3) and 1,3-[(Ph3P)2(η5-C5H5)OsCt C]2-
5-[(CO)3(Cl)Re(bpyCt C)]C6H3 (18) (Fc ) (η5-C5H5)(η5-C5H4)Fe; Rc ) (η5-C5H5)(η5-C5H4)Ru; tBu2bpy
) 4,4′-di-tert-butyl-2,2′-bipyridyl; bpy ) 2,2′-bipyridyl-5-yl) in the solid state is reported. Both compounds
are characterized by the central 1,3,5-triethynylbenzene core, bridging the individual transition metal
building blocks. These organometallic fragments show thereby typical structural properties. The appropriate
metal acetylide moieties are, as expected, found in a linear arrangement with representative M-C and
Ct C bond distances.
available.9c Very recently this family of complexes was enriched
by diverse iron, ruthenium, osmium, rhenium, and platinum
Introduction
organometallic termini.10 One of these molecules is 1-(FcCt C)-
3-[(tBu2bpy)(CO)3ReCt C]-5-[trans-(Ph3P)2(Cl)PtCt C]C6H3
(tBu2bpy ) 4,4′-di-tert-butyl-2,2′-bipyridyl), which can be used
as a suitable starting material in the preparation of heterometallic
complexes of higher nuclearity.10 The Pt-Cl functionality
facilitates the formation of unsymmetrical platinum(II) bis-
acetylides and consequently the connection to further organic
Due to their active coordination sites, all-carbon ligands,
aryldiethynyls, arylethenyls, alkynylthiophenes, etc., are of
particular importance in the synthesis of a huge number of rigid-
rod-structured carbon-rich π-conjugated homo- and heterome-
tallic transition metal complexes.1–7 Especially, the 1,3,5-
triethynylbenzene core allows the design of organometallics that
can be extended in three directions.8,9 Hitherto, mainly homo-
trimetallic systems incorporating, for example, [(R3P)Au] and
[(η5-C5Me5)(η2-dppe)Fe] (dppe ) bis(diphenylphosphino)et-
hane) building blocks exist, while less is known about hetero-
metallic derivatives.8,9 A short while ago, only one example
with three different metal-containing building blocks such as
Fc, [(η2-dppm)2OsCl], and (η2-dppm)2RuCl] (Fc ) (η5-C5H5)(η5-
(3) Homometallic systems with aryldiethynyl bridges: (a) Chawdhury,
N.; Long, N. J.; Mahon, M. F.; Ooi, L.; Raithby, P. R.; Rooke, S.; White,
A. J. P.; Williams, D. J.; Younus, M. J. Organomet. Chem. 2004, 689,
840. (b) de Montigny, F.; Argouarch, G.; Costuas, K.; Halet, J. F.; Roisnel,
T.; Toupet, L.; Lapinte, C. Organometallics 2005, 24, 4558. (c) Callejas-
Gaspar, B.; Laubender, M.; Werner, H. J. Organomet. Chem. 2003, 684,
144. (d) Klein, A.; Lavastre, O.; Fiedler, J. Organometallics 2006, 25, 635.
(e) Hurst, S. K.; Cifuentes, M. P.; McDonagh, A. M.; Humphrey, M. G.;
Samoc, M.; Luther-Davies, B.; Asselberghs, I.; Persoons, A. J. Organomet.
Chem. 2002, 642, 259. (f) Hurst, S. K.; Ren, T. J. Organomet. Chem. 2002,
660, 1. (g) Fraysse, S.; Coudret, S.; Launay, J. P. J. Am. Chem. Soc. 2003,
125, 5880. (h) Back, S.; Lutz, M.; Spek, A. L.; Lang, H.; van Koten, G. J.
Organomet. Chem. 2001, 620, 227. (i) Weyland, T.; Ledoux, I.; Brasselet,
S.; Zyss, J.; Lapinte, C. Organometallics 2000, 19, 5235. (j) Colbert,
M. C. B.; Lewis, J.; Long, N. J.; Raithby, P. R.; Younus, M.; White, A. J. P.;
Williams, D. J.; Payne, N. N.; Yellowlees, L.; Beljonne, D.; Chawdhury,
N.; Friend, R. H. Organometallics 1998, 17, 3034. (k) Bruce, M. I.; Hall,
B. C.; Kelly, B. D.; Low, P. J.; Skelton, B. W.; White, A. H. J. J. Chem.
Soc., Dalton Trans. 1999, 3719. (l) Lavastre, O.; Even, M.; Dixneuf, P. H.;
Pacreau, A.; Vairon, J. Organometallics 1996, 15, 1530. (m) Vicente, J.;
Chicote, M. T.; Alvarez-Falcon, M. M.; Bautista, D. Organometallics 2004,
23, 5707. (n) Vicente, J.; Chicote, M. T.; Abrisqueta, M. D.; Alvarez-Falcon,
M. M. J. Organomet. Chem. 2002, 663, 40. (o) Vicente, J.; Chicote, M. T.;
Alvarez-Falcon, M. M.; Jones, P. G. Chem. Commun. 2004, 2658. (p)
Vicente, J.; Chicote, M. T.; Abrisqueta, M. D.; Alvarez-Falcon, M. M.;
Ramirez de Arellano, M. C.; Jones, P. G. Organometallics 2003, 22, 4327.
(q) Vicente, J.; Chicote, M. T.; Alvarez-Falcon, M. M.; Abrisqueta, M. D.;
Hernandez, F. J.; Jones, P. G. Inorg. Chim. Acta 2003, 347, 67. (r) Irwin,
M. J.; Vittal, J. J.; Puddephatt, R. J. Organometallics 1997, 16, 3541. (s)
Wong, W.-Y.; Choi, K.-H.; Lu, G.-L.; Shi, J.-X.; Lai, P.-Y.; Chan, S.-M.;
Lin, Z. Organometallics 2001, 20, 5446. (t) Onitsuka, K.; Yamamoto, S.;
Takahashi, S. Angew. Chem., Int. Ed. 1999, 38, 174.
C5H4)Fe; dppm
) bis(diphenylphosphino)methane) was
* Corresponding author. E-mail: heinrich.lang@chemie.tu-chemnitz.de.
(1) Homobimetallic systems with all-carbon bridges: (a) Bruce, M. I.;
Low, P. J. AdV. Organomet. Chem. 2004, 50, 179. (b) Szafert, S.; Gladysz,
J. A. Chem. ReV. 2006, 106, PR1–PR33. (c) Bruce, M. I.; Jevric, M.; Skelton,
B. W.; Smith, M. E.; White, A. H.; Zaitseva, N. N. J. Organomet. Chem.
2006, 691, 361. (d) Maurer, J.; Winter, R. F.; Sarkar, B.; Zalis, S. J. Solid
State Electrochem. 2005, 9, 738. (e) Meyer, W. E.; Amoroso, A. J.; Horn,
C. R.; Jaeger, M.; Gladysz, J. A. Organometallics 2001, 20, 1115. (f)
Dembinski, R.; Bartik, T.; Jaeger, M.; Gladysz, J. A. J. Am. Chem. Soc.
2000, 122, 810.
(2) Heterobimetallic systems with all-carbon bridges:(a) Bruce, M. I.;
Costuas, K.; Davin, T.; Ellis, B. G.; Halet, J. F.; Lapinte, C.; Low, P. J.;
Smith, M. E.; Skelton, B. W.; Toupet, L.; White, A. H. Organometallics
2005, 24, 3864. (b) Bruce, M. I.; Humphrey, P. A.; Jevric, M.; Skelton,
B. W.; White, A. H. J. Organomet. Chem. 2007, 692, 2564. (c) Bruce,
M. I.; Costuas, K.; Ellis, B. G.; Halet, J.-F.; Low, P. J.; Moubaraki, B.;
Murray, K. S.; Ouddai, N.; Perkins, G. J.; Skelton, B. W.; White, A. H.
Organometallics 2007, 26, 3735. (d) Bruce, M. I.; Hall, B. C.; Low, P. J.;
Smith, M. E.; Skelton, B. W.; White, A. H. Inorg. Chim. Acta 2000, 300
(302), 633. (e) Bruce, M. I.; Smith, M. E.; Skelton, B. W.; White, A. H. J.
Organomet. Chem. 2001, 637 (639), 484. (f) Jiao, H.; Costuas, K.; Gladysz,
J. A.; Halet, J.-F.; Guillemot, M.; Toupet, L.; Paul, F.; Lapinte, C. J. Am.
Chem. Soc. 2003, 125, 9511.
10.1021/om800232m CCC: $40.75
2008 American Chemical Society
Publication on Web 06/14/2008

Unsymmetrical Platinum(II) Bis-acetylide Complexes
Organometallics, Vol. 27, No. 14, 2008 3535
Scheme 1. Reaction Scheme for the Synthesis of Tetrametallic 3 and Pentanuclear 7
and organometallic groups, which additionally can possess
pendent coordination sites.
η5-C5H4SiMe3)2Ti). On replacement of acetonitrile by the 2,2′-
bipyridyl ligand, the heteropentametallic molecule 7, featuring the
transition metals Ti, Re, Fe, Pt, and Cu, was obtained as a red
material in high yield (Scheme 1).
Multimetallic 3 and 5 are stable both in the solid state and in
solution, while 7 slowly starts to decompose in solution over
prolonged time.
In the frame of our previous work in this field of chemistry,
we report herein the consecutive synthesis, characterization, and
structure of heterotri- to heteroheptametallic transition metal
complexes and, hence, enrich this family of novel compounds
in a straightforward way.
The identities of 3, 5, and 7 have been confirmed by elemental
analysis, IR, 1H and 31P{1H} NMR spectroscopy, and ESI-TOF
mass spectrometry. The structure of 3 in the solid state was
additionally determined by single-crystal X-ray structure analy-
sis, thus confirming the structural assignment made from
spectroscopic characterization.
Results and Discussion
In order to synthesize heteromultimetallic complexes based
on a bis-acetylide platinum(II) connecting unit we choose
1-(FcCt C)-3-[(t Bu2 bpy)(CO)3 ReCt C]-5-[trans-
(Ph3P)2(Cl)PtCt C]C6H3 (1)10 as key starting material. In
general, the preparation of the unsymmetrical Pt(II) bis-
acetylides was envisaged by using the dehydrohalogenation
methodology introduced by Russo et al.11 The monoacetylide
complex 1 was obtained from 1-(FcCt C)-3-[(tBu2bpy)(CO)3-
ReCt C]-5-(HCt C)C6H3 and cis-[(Ph3P)2PtCl2] using chloro-
form as solvent in the presence of a small amount of diethy-
lamine, which avoided the formation of significant amounts of
the corresponding symmetric bis-acetylide complex.10
(4) Heterometallic systems with aryldiethynyl bridges: (a) Lam, S. C. F.;
Yam, V. W. W.; Wong, K. M. C.; Cheng, E. C. C.; Zhu, N. Organometallics
2005, 24, 4298. (b) Wong, K. M. C.; Lam, S. C. F.; Ko, C. C.; Zhu, N.;
Yam, V. W. W.; Roue´, S.; Lapinte, C.; Fathallah, S.; Costuas, K.; Kahlal,
S.; Halet, J. F. Inorg. Chem. 2003, 42, 7086. (c) Younus, M.; Long, N. J.;
Raithby, P. R.; Lewis, J. J. Organomet. Chem. 1998, 570, 55. (d) Lavastre,
O.; Plass, J.; Bachmann, P.; Guesmi, S.; Moinet, C.; Dixneuf, P. H.
Organometallics 1997, 16, 184. (e) Samoc, M.; Gauthier, N.; Cifuentes,
M. P.; Paul, F.; Lapinte, C.; Humphrey, M. G. Angew. Chem., Int. Ed. 2006,
45, 7376.
Unsymmetrical 1-(FcCt C)-3-[(tBu2bpy)(CO)3ReCt C]-5-
[trans-(Ph3P)2(RcCt C)PtCt C]C6H3 (3) and 1-(FcCt C)-3-
[(tBu2bpy)(CO)3ReCt C]-5-[trans-(Ph3P)2(bpyCt C)PtCt C]-
C6H3 (5) (Rc ) (η5-C5H5)(η5-C5H4)Ru; bpy ) 2,2′-bipyridyl-
5-yl) were accessible by reacting 1 with 1.5 equiv of
ethynylruthenocene (2) and 5-ethynyl-2,2′-bipyridyl (4), respec-
tively (Scheme 1). It is necessary to add a catalytic quantity of
[CuI] to the chloroform-diethylamine reaction medium. After
appropriate workup, complexes 3 and 5 could be isolated as
yellow- to orange-colored solids in good yield (Experimental
Section).
(5) (a) Mata, J. A.; Peris, E.; Llusar, R.; Uriel, S.; Cifuentes, M. P.;
Humphrey, M. G.; Samoc, M.; Luther-Davies, B. Eur. J. Inorg. Chem. 2001,
2113. Systems with arylethenyl bridges: (b) Xia, H.; Wen, T. B.; Hu, Q. Y.;
Wang, X.; Chen, X.; Shek, L. Y.; Williams, I. D.; Wong, K. S.; Wong,
G. K. L.; Jia, G. Organometallics 2005, 24, 562. (c) Briel, O.; Fehn, A.;
Beck, W. J. Organomet. Chem. 1999, 578, 247. (d) Mata, J. A.; Peris, E.
Inorg. Chim. Acta 2003, 343, 175. (e) Mu¨ller, T. J. J. Organomet. Chem.
1999, 578, 95. (f) Maurer, J.; Sarkar, B.; Kaim, W.; Winter, R. F.; Za´lisˇ, S.
Chem.-Eur. J. 2007, 13, 10257.
(6) Homometallic systems with 2,5-diethynylthiophene:(a) Le Stang, S.;
Paul, F.; Lapinte, C. Organometallics 2000, 19, 1035. (b) Zhu, Y.; Wolf,
M. O. J. Am. Chem. Soc. 2000, 122, 10121. (c) Viola, E.; Lo Sterzo, C.;
Crescenzi, R.; Frachey, G. J. Organomet. Chem. 1995, 493, C9.
(7) Heterometallic systems with 2,5-diethynylthiophene:(a) Jacques, B.;
Tranchier, J. P.; Rose-Munch, F.; Rose, E.; Stephenson, G. R.; Guyard-
Duhayon, C. Organometallics 2004, 23, 184. (b) Wong, W. Y.; Lu, G. L.;
Ng, K. F.; Choi, K. H.; Lin, Z. J. Chem. Soc., Dalton Trans. 2001, 22,
3250. (c) Viola, E.; Lo Sterzo, C.; Trezzi, F. Organometallics 1996, 15,
4352.
The presence of an N-ligating moiety in 5 allows the complex-
ation of further organometallic complex fragments, and hence,
complex 5 was reacted with the organometallic Ti-Cu π-tweezer
molecule [{[Ti](µ-σ,π-Ct CSiMe3)2}Cu(Nt CMe)]PF6 (6) ([Ti] )

3536 Organometallics, Vol. 27, No. 14, 2008
Packheiser et al.
The IR spectra of all complexes are characterized by the
νCt CPt vibrations in the range of 2097-2106 cm-1; the position
of this band is shifted toward lower frequencies compared to
Hz, in agreement with the values found in other square-planar
platinum complexes with trans-geometry.11,15
The consecutive building of higher nuclear heterometallic
assemblies from 1 is also confirmed by 1H NMR spectroscopic
studies, since the resonance signals for the new introduced
organometallic fragments can nicely be seen (Experimental
Section). The successful formation of 3 and 5 is best reflected
by a significant upfield shift of the Rc and bpy protons adjacent
to the alkynyl moiety. For example, the resonance signal of H4/
bpy is shifted from 7.89 (4) to 6.62 (5) ppm.
monoacetylide 1.10,11 The predictable weak νCt vibration at
C
titanium (1925 cm-1 12
)
in 7 is covered by the three intense
carbonyl absorptions typical for the [(tBu2bpy)(CO)3Re] building
block (Experimental Section).4b,9b,13
In the 31P{1H} NMR spectra of 3, 5, and 7, when compared
to 1,10 an upfield shift is observed (1: 20.5 ppm; 5: 17.7 ppm).
The magnitude of 1J
Pt is known to act as a useful probe of
31P195
the geometry of any present isomer in square-planar Pt(II)
The formation of 3, 5, and 7 is additionally evidenced from
ESI-TOF mass spectrometric investigations, indicating the
presence of molecular ions [M + H]+ (3, 5) or [M - PF6]+ (7)
(Experimental Section).
complexes.14 The 1J
Pt value of 3, 5, and 7 is, at 2612-2664
31P195
(8) Homometallic systems with 1,3,5-triethynylbenzene: (a) Fink, H.;
Long, N. J.; Martin, A. J.; Opromolla, G.; White, A. J. P.; Williams, D. J.;
Zanello, P. Organometallics 1997, 16, 2646. (b) Weyland, T.; Costuas, K.;
Mari, A.; Halet, J. F.; Lapinte, C. Organometallics 1998, 17, 5569. (c)
Tykwinski, R. R.; Stang, P. J. Organometallics 1994, 13, 3203. (d) Mu¨ller,
T. J. J.; Lindner, H. J. Chem. Ber. 1996, 129, 607. (e) Irwin, M. J.;
Manojlovic-Muir, L.; Muir, K. W.; Puddephatt, R. J.; Yufit, D. S. Chem.
Commun. 1997, 219. (f) Leininger, S.; Stang, P. J.; Huang, S. Organome-
tallics 1998, 17, 3981. (g) Cifuentes, M. P.; Powell, C. E.; Morrall, J. P.;
McDonagh, A. M.; Lucas, N. T.; Humphrey, M. G.; Samoc, M.; Houbrechts,
S.; Asselberghs, I.; Clays, K.; Persoons, A.; Isoshima, T. J. Am. Chem.
Soc. 2006, 128, 10819. (h) Samoc, M.; Morrall, J. P.; Dalton, G. T.;
Cifuentes, M. P.; Humphrey, M. G. Angew. Chem., Int. Ed. 2007, 46, 731.
(i) Powell, C. E.; Morrall, J. P.; Ward, S. A.; Cifuentes, M. P.; Notaras,
E. G. A.; Samoc, M.; Humphrey, M. G. J. Am. Chem. Soc. 2004, 126,
12234. (j) McDonagh, A. M.; Powell, C. E.; Morrall, J. P.; Cifuentes, M. P.;
Humphrey, M. G. Organometallics 2003, 22, 1402. (k) Weyland, T.;
Costuas, K.; Toupet, L.; Halet, J.-F.; Lapinte, C. Organometallics 2000,
19, 4228. (l) Whittall, I. R.; Humphrey, M. G.; Houbrechts, S.; Maes, J.;
Persoons, A.; Schmid, S.; Hockless, D. C. R. J. Organomet. Chem. 1997,
544, 277. (m) Vicente, J.; Chicote, M. T.; Alvarez-Falcon, M. M.; Jones,
P. G. Organometallics 2005, 24, 5956. (n) Onitsuka, K.; Fujimoto, M.;
Ohshiro, N.; Takahashi, S. Angew. Chem., Int. Ed. 1999, 38, 689.
(9) (a) Vicente, J.; Chicote, M. T.; Alvarez-Falcon, M. M. Organome-
tallics 2005, 24, 2764. Heterometallic systems with 1,3,5-triethynylbenzene:
(b) Chong, S. H. F.; Lam, S. C. F.; Yam, V. W. W.; Zhu, N.; Cheung,
K. K.; Fathallah, S.; Costuas, K.; Halet, J. F. Organometallics 2004, 23,
4924. (c) Long, N. J.; Martin, A. J.; White, A. J. P.; Williams, D. J.; Fontani,
M.; Laschi, F.; Zanello, P. J. Chem. Soc., Dalton Trans. 2000, 3387. (d)
Long, N. J.; Martin, A. J.; De Biani, F. F.; Zanello, P. J. Chem. Soc., Dalton
Trans. 1998, 2017. (e) Powell, C. E.; Cifuentes, M. P.; Humphrey, M. G.;
Willis, A. C.; Morrall, J. P.; Samoc, M. Polyhedron 2007, 26, 284.
(10) Packheiser, R.; Ecorchard, P.; Ru¨ffer, T.; Lohan, M.; Justaud, F.;
Lapinte, C.; Lang, H. Organometallics 2008, in press.
(11) (a) Furlani, A.; Licoccia, S.; Russo, M. V.; Chiesi Villa, A.;
Guastini, C. J. Chem. Soc., Dalton Trans. 1984, 2197. (b) Russo, M. V.;
Furlani, A.; Licoccia, S.; Paolesse, R.; Chiesi-Villa, A.; Guastini, C. J.
Organomet. Chem. 1994, 469, 245. (c) D’Amato, R.; Furlani, A.; Colapietro,
M.; Portalone, G.; Casalboni, M.; Falconieri, M.; Russo, M. V. J.
Organomet. Chem. 2001, 627, 13. (d) D’Amato, R.; Fratoddi, I.; Cappotto,
A.; Altamura, P.; Delfini, M.; Bianchetti, C.; Bolasco, A.; Polzonetti, G.;
Russo, M. V. Organometallics 2004, 23, 2860. (e) Russo, M. V.; Lo Sterzo,
C.; Franceschini, P.; Biagini, G.; Furlani, A. J. Organomet. Chem. 2001,
619, 49.
(12) (a) Packheiser, R.; Walfort, B.; Lang, H. Organometallics 2006,
25, 4579. (b) Packheiser, R.; Lang, H. Inorg. Chem. Commun. 2007, 10,
580. (c) Lang, H.; George, D. S. A.; Rheinwald, G. Coord. Chem. ReV.
2000, 206 (207), 101. (d) Lang, H.; Ko¨hler, K.; Blau, S. Coord. Chem.
ReV. 1995, 143, 113.
Single crystals of 3 were obtained from diffusion of n-pentane
into a dichloromethane/chloroform solution containing 3 at room
temperature. The molecular structure of 3 together with selected
bond distances (Å) and angles (deg) is presented in Figure 1.
The crystal and structure refinement data are summarized in
Table 1 (Experimental Section).
Complex 3 represents a heterometallic Fe-Re-Pt-Ru
compound in which four different metal building blocks are
connected via a 1,3,5-triethynylbenzene core (Figure 1). The
structure of 3 shows a somewhat distorted octahedral geometry
about Re1 with three carbonyl ligands arranged in a facial
fashion. As required by the bite distance exerted by the steric
demand of the chelating bipyridyl ligand, the N1-Re1-N2
angle is, at 74.3(2)°, conspicuously smaller than 90° (Figure
1).13 The Pt1 center with its d8-electron configuration possesses
a slightly distorted square-planar coordination geometry (rms
deviation 0.0275 Å), as can be seen from the angles around
Pt1 with a linear trans-oriented Ct C-Pt-Ct C arrangement
(Figure 1). The deviation from an ideal square-planar arrange-
ment can be explained by steric interactions between the bulky
groups around Pt1. A similar behavior was also observed for,
e.g., trans-[(PEt2Ph)2(Cl)Pt(Ct CPh)].15c The coordination plane
around Pt1 forms an interplanar angle of 32.73(0.22)° with the
central phenylene ring. The two cyclopentadienyls of the
metallocene units are found in an almost eclipsed conformation
(Fc, 1.64(0.43)°; Rc, 7.33(0.71)°). In relation to the central C6H3
ring the ferrocene and ruthenocene moieties are located on
different sides, whereby the angles between the respective
cyclopentadienyl units and the phenyl ring are 34.27(0.37)° (Fc)
and 6.59(0.49)° (Rc). The three alkynyl bonds at the phenylene
core and the Ct C triple bond in the ethynyl linkage to the
ruthenocene unit are in the range 1.201(10)-1.216(11) Å and
are comparable to those found for other triethynylbenzene
organometallic systems.8,9
A further possibility to prepare heteromultimetallic complexes
is given by the linkage of two different substituted 1,3,5-
triethynylbenzene molecules via a platinum atom. For this
purpose we choose 1-(FcCt C)-3-[(tBu2bpy)(CO)3ReCt C]-5-
[trans-(Ph3P)2(Cl)PtCt C]C6H3 (1). The synthesis methodology
of the second building block to be introduced, 1-[(Ph3P)2(η5-
C5H5)OsCt C]-3-(bpyCt C)-5-(HCt C)C6H3 (13), is displayed
in Scheme 2.
For the overall synthesis of 13 1-iodo-3,5-dibromobenzene
(8) was used as suitable starting material because the more
reactive aryl-iodo bond allowed a selective introduction of a
5-ethynyl-2,2′-bipyridyl moiety following the Sonogashira cross-
coupling protocol.16 Thus formed 9 further reacted with an
excess of trimethylsilylacetylene under similar reaction condi-
(13) (a) Yam, V. W. W.; Wong, K. M. C.; Chong, S. H. F.; Lau,
V. C. Y.; Lam, S. C. F.; Zhang, L.; Cheung, K. K. J. Organomet. Chem.
2003, 670, 205. (b) Yam, V. W. W.; Chong, S. H. F.; Ko, C. C.; Cheung,
K. K. Organometallics 2000, 19, 5092. (c) Yam, V. W. W.; Lau, V. C. Y.;
Cheung, K. K. Organometallics 1996, 15, 1740. (d) Yam, V. W. W. Chem.
Commun. 2001, 789.
(14) Pregosin, P. S.; Kunz, R. W., Eds. 31P- and 13C-NMR of Transition
Metal Phosphine Complexes; Springer Verlag: Berlin, 1976.
(15) (a) Cross, R. J.; Davidson, M. F. J. Chem. Soc., Dalton Trans.
1986, 1987. (b) Bhattacharyya, P.; Sheppard, R. N.; Slawin, A. M. Z.;
Williams, D. J.; Woollins, J. D. J. Chem. Soc., Dalton Trans. 1993, 2393.
(c) Cardin, C. J.; Cardin, D. J.; Lappart, M. F. K.; Muir, W. J. Chem. Soc.,
Dalton Trans. 1978, 46. (d) Bruce, M. I.; Davy, J.; Hall, B. C.; van Galen,
Y. J.; Skelton, B. W.; White, A. H. Appl. Organometal. Chem. 2002, 16,
559. (e) Campbell, K.; McDonald, R.; Ferguson, M. J.; Tykwinski, R. R.
J. Organomet. Chem. 2003, 683, 379. (f) Bosch, E.; Barnes, C. L.
Organometallics 2000, 19, 5522. (g) Campbell, K.; McDonald, R.; Ferguson,
M. J.; Tykwinski, R. R. Organometallics 2003, 22, 1353.
(16) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975,
50, 4467.

Unsymmetrical Platinum(II) Bis-acetylide Complexes
Organometallics, Vol. 27, No. 14, 2008 3537
Figure 1. Perspective drawing of complex 3. Thermal ellipsoids are shown at the 30% probability level. The hydrogen atoms, three molecules
of chloroform, one dichloromethane, and one molecule of water are omitted for clarity. Selected bond distances (Å) and angles (deg):
C7-C8, 1.215(11); Fe1-D1, 1.639(4); Fe1-D2, 1.650(4); C19-C20, 1.216(11); Re1-C20, 2.111(8); Re1-N1, 2.176(6); Re1-N2, 2.163(7);
Re1-C21, 1.922(10); Re1-C22, 1.896(9); Re1-C23, 1.925(9); C21-O1, 1.157(11); C22-O2, 1.171(11); C23-O3, 1.180(10); C42-C43,
1.201(10); Pt1-C43, 1.993(7); Pt1-C80, 2.003(7); C80-C81, 1.212(10); Pt1-P1, 2.3110(18); Pt1-P2, 2.3030(18); Ru1-D1, 1.812(4);
Ru1-D2, 1.819(4); C5-C7-C8, 173.4(9); C7-C8-C9, 178.8(10); C3-C19-C20, 174.3(8); C19-C20-Re1, 166.1(6); N1-Re1-N2,
74.3(2); C20-Re1-C23, 172.0(3); Re1-C21-O1, 179.2(8); Re1-C22-O2, 176.6(9); Re1-C23-O3, 177.6(8); C1-C42-C43, 176.6(8);
C42-C43-Pt1, 175.6(6); C43-Pt1-C80, 178.9(3); Pt1-C80-C81, 176.7(6); C80-C81-C82, 177.1(8); P1-Pt1-P2, 177.95(6); (D1 )
centroid of C9-C13; D2 ) centroid of C14-C18; D3 ) centroid of C82-C86; D4 ) centroid of C87-C91).
tions to produce 10, whose desilylation with [nBu4N]F gave 11
as a colorless solid (Scheme 2). The last step in the preparation
of 13 included the dehydrohalogenation of 11 with [(Ph3P)2(η5-
C5H5)OsBr] (12) in the presence of [NH4]PF6 followed by
deprotonation of the intermediate formed osmium vinylidene
species by addition of sodium to the methanolic solution. Within
this reaction, compound 13 was produced together with di-
nuclear 14 (Scheme 2), which could be separated by column
chromatography (Experimental Section).
Combining molecule 1 with 13 under similar reaction
conditions described in the synthesis of 3 and 5 (vide supra)
gave heterotetrametallic 15, which, after appropriate workup,
could be isolated as fairly stable orange-colored solid in 72%
yield (Scheme 3). Complex 15 bears a free 2,2′-bipyridyl entity,
which can be further reacted with the organometallic π-tweezer
molecule 6 to form complex 16, in which six different transition
metals are held together by two 1,3,5-triethynylbenzene con-
necting units (Scheme 3).
Since homodinuclear 14 also features a noncoordinated 2,2′-
bipyridyl unit, this molecule was treated with equimolar amounts
of [Re(CO)5Cl] (17) to give the trimetallic Os2Re species 18
(eq 1, Experimental Section).
Single crystals of 18 suitable for X-ray crystallography were
obtained from slow diffusion of n-pentane into a dichlo-
romethane solution containing 18 at 25 °C (Figure 2, Table 1).
In 18 a triethynylbenzene moiety connects two [(Ph3P)2(η5-
C5H5)Os] fragments with one [(bpy)(CO)3ClRe] building block.
As typical for 3 (Figure 1) the rhenium atom in 18 adopts a
somewhat distorted octahedral coordination sphere with facial
oriented carbonyl ligands. The bond distances and angles of
this unit are characteristic for this type of organometallic
fragment.9b,13 The bpy-Re plane (rms deviation 0.0105 Å)
forms an interplanar angle of 19.73(0.33)° with the central
phenylene ring. The osmium atoms are pseudotetrahedral
coordinated as commonly found in other piano-stool-structured
complexes.17 The bond angles of Os1-C8-C7 (175.6(8)°),
C1-C7-C8 (173.5(10)°), Os2-C51-C50 (173.3(8)°), and
C3-C50-C51 (175.8(10)°) specify only slightly distorted linear
arrangements, as anticipated for the sp hybridization of the
alkynyl carbon atoms. All other bond lengths and angles are
typical as found in other metal-alkynyl complexes.13,17
Complexes 9-11, 13-16, and 18 were characterized by
elemental analysis, NMR (1H, 31P{1H}), and IR spectroscopy.
Furthermore, ESI-TOF mass spectrometric investigations were
carried out.
In the IR spectra of these complexes the CO and Ct C
stretching vibrations are very diagnostic and represent a useful
(17) (a) Bruce, M. I.; Low, P. J.; Hartl, F.; Humphrey, P. A.; de
Montigny, F.; Jevric, M.; Lapinte, C.; Perkins, G. J.; Roberts, R. L.; Skelton,
B. W.; White, A. H. Organometallics 2005, 24, 5241. (b) Perkins, G. J.;
Bruce, M. I.; Skelton, B. W.; White, A. H. Inorg. Chim. Acta 2006, 359,
2644. (c) Paul, F.; Ellis, B. G.; Bruce, M. I.; Toupet, L.; Roisnel, T.; Costuas,
K.; Halet, J. F.; Lapinte, C. Organometallics 2006, 25, 649. (d) Powell,
C. E.; Cifuentes, M. P.; McDonagh, A. M.; Hurst, S. K.; Lucas, N T.; Delfs,
C. D.; Stranger, R.; Humphrey, M. G.; Houbrechts, S.; Asselberghs, I.;
Persoons, A.; Hockless, D. C. R. Inorg. Chim. Acta 2003, 352, 9.

3538 Organometallics, Vol. 27, No. 14, 2008
Packheiser et al.
Table 1. Crystal and Intensity Collection Data for 3 and 18
3 × 3 CHCl3 × CH2Cl2 × H2O
18 × 2 CHCl3
2406.40
109H82Cl7N2O3Os2P4Re
fw
2305.73
chemical formula
cryst syst
space group
a (Å)
b (Å)
c (Å)
C95H82Cl11FeN2O4P2PtReRu
triclinic
C
triclinic
j
j
P1
P1
11.6644(5)
18.1424(10)
23.1605(13)
101.209(5)
100.387(4)
100.602(4)
4605.5(4)
9.7379(9)
20.428(2)
26.946(3)
75.718(10)
80.444(9)
82.966(9)
5103.7(10)
1.566
R (deg)
ꢀ (deg)
γ (deg)
V (Å3)
Fcalc (g cm-3
F(000)
)
1.663
2276
2360
cryst dimens (mm3)
Z
0.2 × 0.2 × 0.2
0.15 × 0.05 × 0.05
2
2
max., min. transmn
absorp coeff (µ, mm-1
scan range (deg)
index ranges
1.00000, 0.83410
3.545
1.00000, 0.56339
9.543
)
2.83 to 26.06
-14 e h e 14
-22 e k e 22
-28 e l e 28
45 217
3.42 to 60.51
-10 e h e 9
-23 e k e 23
-30 e l e 30
39 189
total no. of reflns
no. of unique reflns
R(int)
17 964
0.0293
14 947
0.0356
no. of data/restraints/params
17 964/21/1085
1.091
0.0475, 0.1309
0.0724, 0.1501
3.864, -2.294
14 947/81/1023
1.038
0.0559, 0.1573
0.0764, 0.1709
3.273, -2.401
goodness-of-fit on F2
R1,a wR2a [I g 2σ(I)]
R1,a wR2a (all data)
max., min. peak in final Fourier map (e Å-3
)
2
2 2
2
2 2
a R1 ) [∑(||Fo| - |Fc||)/∑|Fo|); wR2 ) [∑(w(Fo - Fc ) )/∑(wFo4)]1/2. S )[∑w(Fo - Fc ) ]/(n - p)1/2. n ) number of reflections, p ) parameters
used.
Scheme 2. Synthesis of 13 and 14
monitoring tool (for example, 18: 1894, 1918, 2019 (νCO), 2059
based complexes and reflect the resonance signals for each
individual organic and organometallic building block (Experi-
mental Section).
(νCt COs), 2203 (νCt Cbpy)) along with the appearance and
disappearance of the ν≡C-H absorption. Noteworthy is that the
intensity of the νCt C stretching vibrations can vary, and in some
of the complexes not all of the expected bands are observed
(Experimental Section).
For 15, 16, and 18 ESI-TOF mass spectrometry indicated
the presence of molecular ions with characteristic isotope
distributions patterns, verifying the structural composition of
the appropriate organometallic assemblies (Experimental Sec-
tion).
Using the latter synthesis approach (Scheme 3) also unique
heteroheptametallic transition metal complexes should be avail-
able upon replacement of one mononuclear fragment in 16 by
a heterobimetallic building block. One possibility to realize this
is given by the substitution of the ferrocenyl unit by the
heterobimetallic fragment [(η2-dppf)(η5-C5H5)Ru] (dppf ) 1,1′-
bis(diphenylphosphino)ferrocene). To implement this synthesis
approach first heterotetrametallic Fe-Ru-Re-Pt (26) had to
be prepared by applying the consecutive reaction sequence
shown in Scheme 4.
The 31P{1H} NMR spectra of 13-16 and 18 display one
resonance signal at ca. 0.5 ppm due to the presence of the
[(Ph3P)2(η5-C5H5)Os] unit(s) and a signal centered at 17.5 ppm
for the unsymmetrical bis(triphenylphosphine) platinum(II) bis-
acetylide moiety. As in 3, 5, and 7 the platinum atom in 15 and
16 possesses a trans-configuration as derived from the 1J
31P195Pt
coupling constant (2645, 2650 Hz). However, coordination of
the 2,2′-bipyridyl ligand to the transition metal fragments in 16
and 18 does not influence the position of these signals
(Experimental Section).
1
The H NMR spectra of 13-16 and 18 are consistent with
their formulation as heteromultimetallic 1,3,5-triethynylbenzene-

Unsymmetrical Platinum(II) Bis-acetylide Complexes
Organometallics, Vol. 27, No. 14, 2008 3539
Scheme 3. Synthesis of 15 and 16 from 1, 6, and 13
organometallic Ru2Fe2Re compound 1-[(tBu2bpy)(CO)3ReCt C]-
3,5-[(η2-dppf)(η5-C5H5)RuCt C]2C6H3 (24) is formed, in which
two [(η2-dppf)(η5-C5H5)Ru] moieties and a [(tBu2bpy)(CO)3Re]
fragment are bridged via a triethynylbenzene core (Experimental
Section).
As in the modular synthesis of hexametallic 16, the linking
of two triethynylbenzene molecules is possible, as it could be
demonstratedbytreatmentof26with1-[(Ph3P)2(η5-C5H5)OsCt C]-
3-(bpyCt C)-5-(HCt C)C6H3 (13) under similar reaction condi-
tions producing pentametallic 27 (Scheme 5).
Organometallic 27 further reacts with the Ti-Cu tweezer
molecule 6 to give novel 28 (Scheme 5), which, after appropriate
workup, could be isolated as an orange solid in high yield.
Complex 28 is the first example of a heteroheptametallic
organometallic molecule in which the metal atoms Fe, Ru, Os,
Re, Pt, Cu, and Ti are bridged by carbon-rich organic units.
Within the structure of 28 two different heterotrimetallic
triethynylbenzene entities are connected via a trans-[(Ph3P)2Pt]
group, thus generating an unsymmetrical bis-acetylide platinum
central core. Molecule 28 is surprisingly very stable in the solid
state, while solutions show the tendency to decompose during
a longer period of time. Nevertheless, a relative fast decomposi-
tion is observed, when solutions containing 28 were exposed
to air.
The synthesis protocol developed to prepare heteromulti-
nuclear 27 and 28 (Scheme 5) is directed to the use of modular-
shaped organometallic building blocks (vide supra). In this
respect, IR and NMR (1H, 31P{1H}) spectroscopy allowed the
monitoring of the progress of the reactions and verified the
structure and composition of the corresponding organometallic
multinuclear assemblies (Experimental Section). In addition,
ESI-TOF mass spectrometric studies were carried out with 26
and 28.
The three-step synthesis procedure to 26 includes the me-
tathesis of monolithiated triethynylbenzene (19-Li) with
[(tBu2bpy)(CO)3ReCl] (20) and the subsequent dehydrohaloge-
nation of 1-[(tBu2bpy)(CO)3ReCt C]-3,5-(HCt C)2C6H3 (21)
with [(η2-dppf)(η5-C5H5)RuCl] (22), followed by treatment of
thus formed 1-[(tBu2bpy)(CO)3ReCt C]-3-[(η2-dppf)(η5-
C5H5)RuCt C]-5-(HCt C)C6H3 (23) with cis-[(Ph3P)2PtCl2] (25)
(Scheme 4, Experimental Section). For the preparation of 21 a
straightforward procedure was used that includes the reaction
of [(tBu2bpy)(CO)3ReCl] (20) with the in situ prepared lithium
acetylide species in refluxing toluene. Compared to the literature,
this approach increased the yield of 21, while the reaction time
decreased.9b Furthermore it must be noted that, when 21 is
reacted with 22, even in a 1:1 stoichiometry, next to 23 the
Most characteristic in the IR spectra of 27 and 28 is the
appearance of νCt C (2064 (νCt COs(Ru)), 2102 (νCt CPt), 2210 cm-1
(νCt Cbpy)), and νCO (1894, 1901, 2003 cm-1) vibrations as

3540 Organometallics, Vol. 27, No. 14, 2008
Scheme 4. Synthesis of Complexes 23 and 26, Respectively
Packheiser et al.
typical for the individual σ-alkynyl organometallic transition
be found (Figure 3). The signal for the [(Ph3P)2Pt] entity shows
an additional coupling to 195Pt (1J
Pt ) 2659 Hz), emphasiz-
31P195
metal fragments.
In the 31P{1H} NMR spectrum of 27 three resonance signals
at 54.0 (Ru dppf), 17.3 (Ph3P Pt), and 0.4 ppm (Ph3P Os) can
ing a trans-configurated bis-acetylide platinum coordination. The
heptanuclear complex 28 shows in addition to these signals a
-
resonance signal for the PF6 counterion, which is split into a
septet (1JPF ) 713 Hz).
1
The H NMR spectroscopic properties of 27 and 28 nicely
correlate with their formulation as heteromultinuclear molecules
based on 1,3,5-triethynylbenzene cores showing the respective
resonance signal patterns for the organic units. Most distinctive
in the proton NMR spectra of both complexes is the appearance
of six separated resonance signals for the central phenylene ring
protons, confirming the different substitution pattern at the two
triethynylbenzene cores (Figure 4). The upfield shift of the C6H3
signals, especially those next to the platnum acetylide moieties,
may be suggestive of the electron-richness of the corresponding
transition metal building blocks, leading to a reduced electron
donation from the alkynyl unit. Furthermore, an influence of
the ring current of the PPh3 phenyl rings cannot be excluded.
All other units show the expected resonance signals charac-
teristic for the appropriate organic and organometallic building
blocks. Upon coordination of the 2,2′-bipyridyl moiety to
copper(I) as given in 28, the separated and well-resolved signals
of this moiety evince up- and downfield shifts forming broad
multiplets. Most expressive for the formation of 28 is the high-
field shift of the Me3SiCt C protons in comparison to 622 upon
coordination of the bipyridyl unit to the organometallic π-tweezer-
stabilized copper(I) center, which can be explained by the ring
current of the chelating bipyridyl. In addition, as a result of the
different chemical environment, the spectrum of 28 reveals two
separated singlets for the cyclopentadienyl-bonded SiMe3
groups.
Figure 2. Perspective drawing of 18 with the atom-numbering
scheme (only the ipso-carbons of the phenyl rings are labeled).
Hydrogen atoms and two molecules of chloroform are omitted for
clarity. Thermal ellipsoids are shown at the 30% probability level.
Selected bond distances (Å) and angles (deg): C7-C8, 1.200(13);
Os1-C8, 2.025(9); Os1-P1, 2.296(2); Os1-P2, 2.307(3); Os1-
D1, 1.885(4); C50-C51, 1.205(14); Os2-C51, 2.007(10); Os2-P3,
2.285(2); Os2-P4, 2.279(2); Os2-D2, 1.899(4); C93-C94,
1.182(15); Re1-N1, 2.159(8); Re1-N2, 2.170(8); Re1-Cl1,
2.339(6);Os1-C8-C7,175.6(8);C1-C7-C8,173.5(10);P1-Os1-P2,
104.39(8); Os2-C51-C50, 173.3(8); C3-C50-C51, 175.8(10);
P3-Os2-P4, 99.07(9); C5-C93-C94, 176.5(13); C93-C94-C96,
178.7(14); N1-Re1-N2, 74.6(3); (D1 ) centroid of C9-C13, D2
) centroid of C52-C56).
The identitiy of 28 was additionally evidenced from mass
spectrometric investigations. The electrospray ionization mass
spectrum (ESI-MS) of 28 shows a ion peak at a mass-to-charge
ratio (m/z) of 3790.2, which corresponds to [M - PF6]+, confirming
the elemental composition and charge state (Figure 5). A further
peak at m/z ) 1895.6 could be identified as the corresponding
2-fold positive charged complex. The base peak at 809.3 and the
one at 749.0 can be assigned to the fragments
[(PPh3)2(C5H5)Os(CO)]+ and [(dppf)(C5H5)Ru(CO)]+, which are

Unsymmetrical Platinum(II) Bis-acetylide Complexes
Scheme 5. Synthesis of 27 and 28
Organometallics, Vol. 27, No. 14, 2008 3541
Figure 3. 31P{1H} NMR spectrum of heteropentametallic 27.
Instruments. Infrared spectra were recorded with a Perkin-Elmer
FT-IR Spectrum 1000 spectrometer. NMR spectra were recorded
with a Bruker Avance 250 spectrometer (1H NMR at 250.12 MHz
and 13C{1H} NMR at 62.86 MHz) in the Fourier transform mode.
Chemical shifts are reported in δ units (parts per million) downfield
from tetramethylsilane (δ ) 0.00 ppm) with the solvent as the
reference signal (CDCl3: 1H NMR, δ ) 7.26; 13C{1H} NMR, δ )
77.16).19 31P{1H} NMR spectra were recorded at 101.255 MHz in
CDCl3 with P(OMe)3 as external standard (δ ) 139.0, rel to H3PO4
(85%) with δ ) 0.00 ppm). ESI-TOF mass spectra were recorded
using a Mariner biospectrometry workstation 4.0 (Applied Biosys-
tems). Microanalyses were performed with a C,H,N-analyzer of
type FlashAE 1112 (Thermo).
typical products of the decomposition of the respective acetylide
complexes in the presence of water and air.18
Experimental Section
General Data. All reactions were carried out under an atmo-
sphere of nitrogen using standard Schlenk techniques. Tetrahydro-
furan, toluene, and n-pentane were purified by distillation from
sodium/benzophenone ketyl; dichloromethane and chloroform were
purified by distillation from calcium hydride. Diethylamine and
diisopropylamine were distilled from KOH; absolute methanol was
obtained by distillation from magnesium.
(18) (a) Bianchini, C.; Casares, J. A.; Peruzzini, M.; Romerosa, A.;
Zanobini, F. J. Am. Chem. Soc. 1996, 118, 4585, and references therein.
(b) Xia, H. P.; Wu, W. F.; Ng, W. S.; Williams, I. D.; Jia, G.
Organometallics 1997, 16, 2940. (c) Le Lagadec, R.; Roman, E.; Toupet,
L.; Muller, U.; Dixneuf, P. H. Organometallics 1994, 13, 5030. (d)
Bianchini, C.; Innocenti, P.; Peruzzini, M.; Romerosa, A.; Zanobini, F.
Organometallics 1996, 15, 272.
(19) Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997,
62, 7512.
(20) (a) Rausch, M. D.; Fischer, E. O.; Grubert, H. J. Am. Chem. Soc.
1960, 82, 76. (b) Rausch, M. D.; Siegel, A. J. Org. Chem. 1969, 34, 1974.

3542 Organometallics, Vol. 27, No. 14, 2008
Packheiser et al.
Synthesis of 1-(FcCt C)-3-[(tBu2bpy)(CO)3 ReCt C]-5-[trans-
(Ph3P)2(bpyCt C)PtCt C]C6H3 (5). To 80 mg (0.049 mmol) of
1 - ( F c C t C ) - 3 - [ ( t B u 2 b p y ) ( C O ) 3 R e C t C ] - 5 - [ t r a n s -
(Ph3P)2(Cl)PtCt C]C6H3 (1) and 13 mg (0.072 mmol) of 5-ethynyl-
2,2′-bipyridyl (4) dissolved in 10 mL of chloroform and 10 mL of
diethylamine was added 1 mg of [CuI]. The resulting reaction
mixture was stirred for 3 h between 40 and 50 °C. After cooling it
to room temperature all volatile materials were removed under
reduced pressure and the residue was purified by column chroma-
tography on silica gel using a mixture of dichloromethane/toluene
(5:1, v/v) as eluent. Evaporation of the solvents under reduced
pressure gave the title compound as an orange solid. Yield: 61 mg
(0.034 mmol, 70% based on 1).
Figure 4. Part of the 1H NMR spectrum (in CDCl3) of heteropen-
tametallic 27 displaying the 6 pseudotriplets (JHH ) 1.6 Hz) for
the central phenylene ring protons.
Anal. Calcd for C91H73FeN4O3P2PtRe (1769.68): C, 61.76; H,
Reagents. 1-(FcCt C)-3-[(tBu2bpy)(CO)3ReCt C]-5-[trans-(Ph3P)2-
(Cl)PtCt C]C6H3,10 ethynylruthenocene,20 5-ethynyl-2,2′-bipyridyl,21
[{[Ti](µ-σ,π-Ct CSiMe3)2}Cu(Nt CMe)]PF6,22 1-iodo-3,5-dibro-
mobenzene,23 trimethylsilylacetylene,24 [(PPh3)2(η5-C5H5)OsBr],25
[Re(CO)5Cl],26 1,3,5-triethynylbenzene,27 [(tBu2bpy)(CO)3ReCl],28
[(η2-dppf)(η5-C5H5)RuCl],29 and cis-[(PPh3)2PtCl2]30 were prepared
according to published procedures. All other chemicals were purchased
from commercial suppliers and were used as received.
4.16; N, 3.17. Found: C, 62.22; H, 4.45; N, 2.96. IR (KBr, cm-1):
1
1895, 2003 (s, νCO), 2106 (m, νCt CPt), 2215 (w, νCt CFc). H NMR
(δ, CDCl3): 1.43 (s, 18 H, tBu), 4.17 (s, 5 H, C5H5), 4.19 (pt, JHH
)
1.9 Hz, 2 H, C5H4), 4.37 (pt, JHH ) 1.9 Hz, 2 H, C5H4), 5.95 (pt, JHH
) 1.6 Hz, 1 H, C6H3), 5.98 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.51 (pt,
3
4
JHH ) 1.6 Hz, 1 H, C6H3), 6.62 (dd, JH4H3 ) 8.2 Hz, JH4H6 ) 2.0
3
3
Hz, 1 H, H4/bpy), 7.19 (ddd, JH5′H4′ ) 7.8 Hz, JH5′H6′ ) 4.8 Hz,
4JH5′H3′ ) 1.0 Hz, 1 H, H5′/bpy), 7.30-7.48 (m, 20 H (C6H5) + 2 H
(H5/tBu2bpy)), 7.63 - 7.85 (m, 10 H (C6H5) + 2 H (H4,H4′/bpy)),
Synthesis of 1-(FcCt C)-3-[(tBu2bpy)(CO)3 ReCt C]-5-[trans-
(Ph3P)2(RcCt C)PtCt C]C6H3 (3). To 60 mg (0.037 mmol) of
1 - ( F c C t C ) - 3 - [ ( t B u 2 b p y ) ( C O ) 3 R e C t C ] - 5 - [ t r a n s -
(Ph3P)2(Cl)PtCt C]C6H3 (1) and 15 mg (0.059 mmol) of ethynyl-
ruthenocene (2) dissolved in 10 mL of chloroform and 10 mL of
diethylamine was added 1 mg of [CuI]. The resulting reaction
mixture was stirred for 4 h between 40 and 50 °C. After cooling to
room temperature all volatiles were removed in an oil-pump
vacuum, and the residue was purified by column chromatography
on silica gel using a mixture of dichloromethane/toluene (5:1, v/v)
as eluent. After removal of the solvents under reduced pressure,
the title compound was obtained as an orange solid. Yield: 50 mg
(0.027 mmol, 73% based on 1).
3
7.92 (d, JH3H4 ) 8.4 Hz, 1 H, H3/bpy), 8.05 (d, JHH ) 1.7 Hz,
H3/tBu2bpy), 8.21 (ddd, 3JH3′H4′ ) 7.8 Hz, 4JH3′H5′ ) 1.0 Hz, 5JH3′H6′
) 1.0 Hz, 1 H, H3′/bpy), 8.59 (ddd, 3JH6′H5′ ) 4.8 Hz, 4JH6′H4′ ) 1.8
5
Hz, JH6′H3′ ) 1 Hz, 1 H, H6′/bpy), 8.97 (d, JHH ) 5.8 Hz,
H6/tBu2bpy). P{1H} NMR (CDCl3): 17.7 (1J
31
) 2629 Hz,
31P195Pt
PtPPh3). MS (ESI-TOF, m/z): 1770.71 [M + H]+.
Synthesis of [1-(FcCt C)-3-[(tBu2bpy)(CO)3 ReCt C]-5-[trans-
(Ph3P)2({[Ti](µ-σ,π-Ct C-SiMe3 )2}Cu-bpyCt C)PtCt C]C6H3]-
PF6 (7). To a solution of 5 (50 mg, 0.028 mmol) in 15 mL of
degassed tetrahydrofuran was added [{[Ti](µ-σ,π-Ct CSi-
Me3)2}Cu(Nt CMe)]PF6 (6) (22 mg, 0.029 mmol) in a single
portion. The reaction solution was allowed to stir for 2.5 h at 25
°C, whereby the color of the solution changed from orange to red.
Afterward, the solvent was removed under reduced pressure. The
remaining residue was redissolved in 2 mL of dichloromethane,
and addition of n-hexane (15 mL) caused the precipitation of 7.
After removal of the supernatant solution, the precipitate was
washed twice with 10 mL portions of diethyl ether and dried in an
oil-pump vacuum to afford 7 as an orange-red solid. Yield: 59 mg
(0.024 mmol, 85% based on 5).
Anal. Calcd for C91H75FeN2O3P2PtReRu (1844.75): C, 59.25; H,
4.10; N, 1.52. Found: C, 59.20; H, 4.60; N, 1.37. IR (KBr, cm-1):
1
1899, 2004 (s, νCO), 2101 (m, νCt CPt), 2212 (w, νCt CFc). H NMR
t
(δ, CDCl3): 1.43 (s, 18 H, Bu), 3,86 (pt, JHH ) 1.6 Hz, 2 H,
C5H4/Rc) 4.16 (s, 5 H, C5H5), 4.17 (s, 7 H, C5H4 + C5H5), 4.18 (pt,
JHH ) 1.9 Hz, 2 H, C5H4/Fc), 4.37 (pt, JHH ) 1.9 Hz, 2 H, C5H4/Fc),
5.95 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.00 (pt, JHH ) 1.6 Hz, 1 H,
C6H3), 6.55 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 7.29 - 7.45 (m, 22 H,
C6H5 + H5/tBu2bpy), 7.69-7.80 (m, 10 H, C6H5), 8.05 (d, JHH
)
Anal. Calcd for C117H117CuF6FeN4O3P3PtReSi4Ti (2495.04): C,
56.32; H, 4.73; N, 2.25. Found: C, 55.97; H, 4.74; N, 2.15. IR (KBr,
cm-1): 1892, 1900, 2002 (s, νCO), 2107 (m, νCt CPt), 2212 (w,
νCt CFc). 1H NMR (δ, CDCl3): -0.56 (s, 18 H, SiMe3), 0.24 (s, 9 H,
1.7 Hz, H3/tBu2bpy), 8.96 (d, JHH ) 5.8 Hz, H6/tBu2bpy). 31P{1H}
NMR (CDCl3): 17.1 (1J
) 2664 Hz, Pt PPh3). MS (ESI-TOF,
31P195Pt
m/z): 1845.45 [M + H]+.
t
SiMe3), 0.28 (s, 9 H, SiMe3), 1.43 (s, 18 H, Bu), 4.17 (s, 5 H,
(21) (a) Grosshenny, V.; Romero, F. M.; Ziessel, R. J. Org. Chem. 1997,
62, 1491. (b) Schwab, P. F. H.; Fleischer, F.; Michl, J. J. Org. Chem. 2002,
67, 443. (c) Polin, J.; Schmohel, E.; Balzani, V. Synthsis 1998, 3, 321.
(22) Janssen, M. D.; Herres, M.; Zsolnai, L.; Spek, A. L.; Grove, D. M.;
Lang, H.; van Koten, G. Inorg. Chem. 1996, 35, 2476.
(23) (a) Baxter, P. N. W. Chem.-Eur. J. 2003, 9, 5011. (b) Lustenberger,
P.; Diederich, F. HelV. Chim. Acta 2000, 83, 2865.
(24) Brandsma, L. PreparatiVe Acetylenic Chemistry; Elsevier-Verlag:
Amsterdam, 1988; p 114.
(25) (a) Wanandi, P. W.; Tilley, T. D. Organometallics 1997, 16, 4299.
(b) Bruce, M. I.; Windsor, N. J. Aust. J. Chem. 1977, 30, 1601. (c) Bruce,
M. I.; Low, P. J.; Skelton, B. W.; Tiekink, E. R. T.; Werth, A.; White,
A. H. Aust. J. Chem. 1995, 48, 1887.
(26) Schmidt, S. P.; Trogler, W. C.; Basolo, F. Inorg. Synth. 1990, 28,
160.
(27) Ohshiro, N.; Takei, F.; Onitsuka, K.; Takahashi, S. Chem. Lett.
1996, 871.
(28) Yam, V. W. W.; Lau, V. C. Y.; Cheung, K. K. Organometallics
1995, 14, 2749.
C5H5), 4.18 (pt, JHH ) 1.9 Hz, 2 H, C5H4), 4.36 (pt, JHH ) 1.9 Hz, 2
H, C5H4), 5.91 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 5.95 (pt, JHH ) 1.6
Hz, 1 H, C6H3), 6.13-6.20 (m, 4 H, C5H4Si), 6.24 (s, 4 H, C5H4Si),
3
6.51 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.79 (dd, JH4H3 ) 8.2 Hz,
4JH4H6 ) 1.8 Hz, 1 H, H4/bpy), 7.27-7.41 (m, 20 H, C6H5), 7.43
3
4
(dd, JH5H6 ) 6 Hz, JH5H3 ) 1.8 Hz, 2 H, H5/tBu2bpy), 7.53-7.60
(m, 2 H, bpy), 7.68-7.79 (m, 10 H, (C6H5) + 1 H (bpy)),
4
8.02-8.17 (m, 2 H, bpy), 8.06 (d, JH3H5 ) 1.8 Hz, 2 H, H3/
tBu2bpy), 8.35-8.42 (m, 2 H, bpy), 8.96 (d, JH6H5 ) 6 Hz, 2 H,
3
H6/tBu2bpy). 31P{1H} NMR (CDCl3): -145.1 (septet, JPF ) 713
1
Hz, PF6), 17.8 (1J
) 2612 Hz, Pt PPh3). MS (ESI-TOF, m/z):
31P195Pt
2349.9 [M - PF6]+, 1175.9 [M - PF6]2+
.
Synthesis of 1,3-Br2-5-(bpyCt C)C6H3 (9). To 800 mg (2.21
mmol) of 1-iodo-3,5-dibromobenzene (8) and 380 mg (2.11 mmol)
of 5-ethynyl-2,2′-bipyridine (4) dissolved in 50 mL of degassed
diisopropylamine were added 45 mg of [(PPh3)2PdCl2] and 20 mg
of [CuI] at 0 °C. The resulting reaction mixture was stirred for 2 h
at this temperature, followed by stirring overnight at 35 °C. After
cooling it to room temperature the suspension was filtered through
(29) (a) Bruce, M. I.; Butler, I. R.; Cullen, W. R.; Koustanonis, G. A.;
Snow, M. R.; Tiekink, E. R. T. Aust. J. Chem. 1988, 41, 963. (b) Lu, X. L.;
Vittal, J. J.; Tiekink, E. R. T.; Tan, G. K.; Kuan, S. L.; Goh, L. Y.; Hor,
T. S. A. J. Organomet. Chem. 2004, 689, 1978.
(30) Jensen, K. A. Z. Anorg. Allg. Chem. 1936, 229, 265.

Unsymmetrical Platinum(II) Bis-acetylide Complexes
Organometallics, Vol. 27, No. 14, 2008 3543
Figure 5. ESI-MS spectra of heteroheptanuclear 28.
a pad of Celite and the filtrate was evaporated to dryness. The
residue was purified by column chromatography on silica gel using
a mixture of diethyl ether and petroleum ether (1:1, v/v) as eluent.
After removal of the solvents under reduced pressure compound 9
was obtained as a colorless solid. Yield: 680 mg (1.64 mmol, 77%
based on 4).
134.7 (CH/C6H3), 135.3 (CH/C6H3), 137.0 (C4′/bpy), 139.4 (C4/
bpy), 149.4 (C6′/bpy), 151.7 (C6/bpy), 155.2 (Ci/bpy), 155.4 (Ci/
bpy).
Synthesis of 1,3-(HCt C)2-5-(bpyCt C)C6H3 (11). To 450 mg
(1.00 mmol) of 1,3-(Me3SiCt C)2-5-(bpyCt C)C6H3 (10) dissolved
in 40 mL of tetrahydrofuran was added 2.2 mL (2.20 mmol) of
[nBu4N]F (1 M solution in tetrahydrofuran) over a period of 10 min
at 0 °C. After stirring this solution for 1 h at ambient temperature all
volatiles were removed under reduced pressure. The remaining
residue was purified by column chromatography on silica gel using a
mixture of diethyl ether/tetrahydrofuran (20:1, v/v) as eluent. The
solvents were removed under reduced pressure, giving a colorless
solid identified as 11. Yield: 260 mg (0.86 mmol, 85% based on 10).
Anal. Calcd for C22H12N2 (304.35): C, 86.82; H, 3.97; N, 9.20.
Anal. Calcd for C18H10Br2N2 (414.10): C, 52.21; H, 2.43; N, 6.77.
Found: C, 51.91; H, 2.11; N, 7.13. Mp: 152 °C. IR (KBr, cm-1):
1
3
2221 (w, νCt C). H NMR (δ, CDCl3): 7.33 (ddd, JH5′H4′ ) 7.6 Hz,
3JH5′H6′ ) 4.7 Hz, 4JH5′H3′ ) 1.0 Hz, 1 H, H5′/bpy), 7.65 (d, 4JHH
)
4
1.6 Hz, 2 H, C6H3), 7.67 (t, JHH ) 1.6 Hz, 1 H, C6H3), 7.84 (ddd,
3JH4′H3′ ) 8.0 Hz, JH4′H5′ ) 7.6 Hz, JH4′H6′ ) 1.8 Hz, 1 H,
3
4
H4′/bpy), 7.92 (dd, 3JH4H3 ) 8.2 Hz, 4JH4H6 ) 2.0 Hz, 1 H, H4/bpy),
3
4
5
8.43 (ddd, JH3′H4′ ) 8.0 Hz, JH3′H5′ ) 1.0 Hz, JH3′H6′ ) 1.0 Hz, 1
3
5
Found: C, 86.32; H, 4.09; N, 9.40. Mp: 168 °C. IR (KBr, cm-1):
H, H3′/bpy), 8.44 (dd, JH3H4 ) 8.2 Hz, JH3H6 ) 1.0 Hz, 1 H,
3
4
5
1
H3/bpy), 8.70 (ddd, JH6′H5′ ) 4.7 Hz, JH6′H4′ ) 1.8 Hz, JH6′H3′
)
2109 (w, νCt CH), 2208 (w, νCt Cbpy), 3284 (s, ν C-H). H NMR (δ,
t
1.0 Hz, 1 H, H6′/bpy), 8.79 (dd, 4JH6H4 ) 2.0 Hz, 5JH6H3 ) 1.0 Hz, 1
H, H6/bpy). 13C{1H} NMR (δ, CDCl3): 89.0 (Ct C), 90.4 (Ct C),
119.4 (C5/bpy), 120.5 (C3/bpy), 121.6 (C3′/bpy), 122.9 (Ci/C6H3),
124.2 (C5′/bpy), 126.1 (Ci/C6H3), 133.2 (CH/C6H3), 134.6 (CH/
C6H3), 137.1 (C4′/bpy), 139.6 (C4/bpy), 149.5 (C6′/bpy), 151.8
(C6/bpy), 155.4 (Ci/bpy), 155.6 (Ci/bpy).
CDCl3): 3.13 (s, 2 H, t C H), 7.32 (ddd, 3JH5′H4′ ) 7.6 Hz, 3JH5′H6′
)
4
4
4.7 Hz, JH5′H3′ ) 1.0 Hz, 1 H, H5′/bpy), 7.58 (t, JHH ) 1.6 Hz, 1
H, C6H3), 7.65 (d, 4JHH ) 1.6 Hz, 2 H, C6H3), 7.86 (ddd, 3JH4′H3′
)
8.0 Hz, 3JH4′H5′ ) 7.6 Hz, 4JH4′H6′ ) 1.8 Hz, 1 H, H4′/bpy), 7.92 (dd,
3JH4H3 ) 8.2 Hz, JH4H6 ) 2.2 Hz, 1 H, H4/bpy), 8.40-8.45 (m, 2
4
3
4
H, H3,H3′/bpy), 8.69 (ddd, JH6′H5′ ) 4.7 Hz, JH6′H4′ ) 1.8 Hz,
4
5
Synthesis of 1,3-(Me3 SiCt C)2-5-(bpyCt C)C6H3 (10). To 600
mg (1.45 mmol) of 1,3-Br2-5-(bpyCt C)C6H3 (9) dissolved in 50
mL of degassed diisopropylamine were added 380 mg (3.88 mmol)
of trimethylsilylacetylene followed by 50 mg of [(PPh3)2PdCl2] and
25 mg of [CuI]. The resulting reaction mixture was stirred overnight
at 50 °C. After cooling it to room temperature the suspension was
filtered through a pad of Celite and the filtrate was evaporated to
dryness. The residue was purified by column chromatography on
alumina using a mixture of diethyl ether/petroleum ether (10:1, v/v)
as eluent. The product was obtained as a colorless solid. Yield:
510 mg (1.14 mmol, 78% based on 9).
5JH6′H3′ ) 1.0 Hz, 1 H, H6′/bpy), 8.80 (dd, JH6H4 ) 2.2 Hz, JH6H3
) 0.8 Hz, 1 H, H6/bpy). 13C{1H} NMR (δ, CDCl3): 78.9 (C′t CH),
81.8 (Ct CH), 87.9 (Ct Cbpy), 91.5 (Ct Cbpy), 119.7 (C5/bpy),
120.5 (C3/bpy), 121.5 (C3′/bpy), 123.2 (Ci/C6H3), 123.5 (Ci/C6H3),
124.1 (C5′/bpy), 135.3 (CH/C6H3), 135.6 (CH/C6H3), 137.0 (C4′/
bpy), 139.5 (C4/bpy), 149.4 (C6′/bpy), 151.8 (C6/bpy), 155.3 (Ci/
bpy), 155.4 (Ci/bpy).
Synthesis of 1-[(Ph3P)2(η5-C5H5)OsCt C]-3-(bpyCt C)-5-
(HCt C)C6H3 (13) and 1,3-[(Ph3P)2(η5-C5H5)OsCt C]2-5-(bpy-
Ct C)C6H3 (14). A mixture of 320 mg (0.37 mmol) of [(PPh3)2(η5-
C5H5)OsBr] (12), 150 mg (0.49 mmol) of 1,3-(HCt C)2-5-
(bpyCt C)C6H3 (11), and 70 mg (0.43 mmol) of [NH4]PF6 was
stirred in 60 mL of methanol for 3 h at reflux. During that time the
orange suspension turned into a clear red solution, which was
afterward cooled to room temperature. Then 20 mg (0.87 mmol)
of sodium metal was added with stirring, forming a yellow
precipitate. The solvent was removed under reduced pressure, and
the residue was purified by column chromatography on alumina,
eluting with diethyl ether/petroleum ether (3:1, v/v). At first,
unreacted 11 was eluted. The following main fraction contained
13. Finally complex 14 was isolated from the third band. Com-
pounds 13 and 14 were isolated as pale yellow solids. Yield: 13,
175 mg (0.16 mmol, 44% based on 12); 14, 160 mg (0.086 mmol,
46% based on 12).
Anal. Calcd for C28H28N2Si2 (448.72): C, 74.95; H, 6.29; N, 6.24.
Found: C, 74.88; H, 6.76; N, 6.26. Mp: 143 °C. IR (KBr, cm-1):
2158 (s, νCt CSi), 2220 (w, νCt Cbpy). 1H NMR (δ, CDCl3): 0.25 (s, 18
H, Si Me3), 7.32 (ddd, 3JH5′H4′ ) 7.6 Hz, 3JH5′H6′ ) 4.7 Hz, 4JH5′H3′
)
4
1.0 Hz, 1 H, H5′/bpy), 7.55 (t, JHH ) 1.6 Hz, 1 H, C6H3), 7.60 (d,
3
3
4JHH ) 1.6 Hz, 2 H, C6H3), 7.83 (ddd, JH4′H3′ ) 8.0 Hz, JH4′H5′
)
7.6 Hz, 4JH4′H6′ ) 1.8 Hz, 1 H, H4′/bpy), 7.90 (dd, 3JH4H3 ) 8.2 Hz,
4JH4H6 ) 2.0 Hz, 1 H, H4/bpy), 8.39-8.44 (m, 2 H, H3,H3′/bpy),
3
4
5
8.69 (ddd, JH6′H5′ ) 4.7 Hz, JH6′H4′ ) 1.8 Hz, JH6′H3′ ) 1.0 Hz, 1
4
5
H, H6′/bpy), 8.78 (dd, JH6H4 ) 2.0 Hz, JH6H3 ) 1.0 Hz, 1 H,
H6/bpy). 13C{1H} NMR (δ, CDCl3): 87.5 (Ct Cbpy), 91.8 (Ct Cbpy),
96.0 (Ct CSi), 103.1 (Ct CSi), 119.8 (C5/bpy), 120.4 (C3/bpy),
121.4 (C3′/bpy), 123.2 (Ci/C6H3), 124.0 (C5′/bpy), 124.0 (Ci/C6H3),

3544 Organometallics, Vol. 27, No. 14, 2008
Packheiser et al.
13: Anal. Calcd for C63H46N2OsP2 (1083.25): C, 69.85; H, 4.28;
orange to red. Afterward all volatiles were removed under reduced
pressure and the residue was redissolved in 2 mL of dichlo-
romethane. Complex 16 was precipitated from this solution by the
addition of 20 mL of n-hexane. After removal of the supernatant
solution the remaining solid was washed twice with 10 mL portions
of diethyl ether and dried in an oil-pump vacuum to afford an
orange-red solid. Yield: 56 mg (0.016 mmol, 84% based on 15).
N, 2.59. Found: C, 69.74; H, 4.47; N, 2.58. IR (KBr, cm-1): 2116
(w, νCt CH), 2061 (s, νCt COs), 2209 (w, νCt Cbpy), 3302 (m, ν C-H).
t
1H NMR (δ, CDCl3): 3.04 (s, 1 H, t C H), 4.42 (s, 5 H, C5H5),
7.07-7.24 (m, 20 H, C6H5), 7.28 (pt, JHH ) 1.6 Hz, 1 H, C6H3),
3
3
4
7.32 (ddd, JH5′H4′ ) 7.5 Hz, JH5′H6′ ) 4.7 Hz, JH5′H3′ ) 1.0 Hz, 1
H, H5′/bpy), 7.34-7.43 (m, 10 H (C6H5) + 2 H (C6H3)), 7.83 (ddd,
3JH4′H3′ ) 8.0 Hz, JH4′H5′ ) 7.5 Hz, JH4′H6′ ) 1.7 Hz, 1 H,
3
4
Anal. Calcd for C168H155CuF6FeN4O3OsP5PtReSi4Ti × CH2Cl2
(3482.96): C, 58.28; H, 4.54; N, 1.61. Found: C, 58.26; H, 4.53; N,
1.61. IR (KBr, cm-1): 1900, 2003 (s, νCO), 2064 (m, νCt COs), 2095
(m, νCt CPt), 2207 (w, νCt CFc). 1H NMR (δ, CDCl3): -0.46 (s, 18 H,
Si Me3), 0.26 (s, 9 H, Si Me3), 0.29 (s, 9 H, Si Me3), 1.43 (s, 18 H,
tBu), 4.17 (s, 5 H, C5H5/Fc), 4.18 (pt, JHH ) 1.9 Hz, 2 H, C5H4),
4.36 (s, 5 H, C5H5/Os), 4.37 (pt, JHH ) 1.9 Hz, 2 H, C5H4), 5.30 (s,
H4′/bpy), 7.94 (dd, 3JH4H3 ) 8.4 Hz, 4JH4H6 ) 2.2 Hz, 1 H, H4/bpy),
3
5
8.43 (dd, JH3H4 ) 8.4 Hz, JH3H6 ) 0.8 Hz, 1 H, H3/bpy), 8.44
3
4
5
(ddd, JH3′H4′ ) 8.0 Hz, JH3′H5′ ) 1.0 Hz, JH3′H6′ ) 1.0 Hz, 1 H,
3
4
5
H3′/bpy), 8.70 (ddd, JH6′H5′ ) 4.7 Hz, JH6′H4′ ) 1.7 Hz, JH6′H3′
)
1.0 Hz, 1 H, H6′/bpy), 8.82 (dd, 4JH6H4 ) 2.2 Hz, 5JH6H3 ) 0.8 Hz, 1
H, H6/bpy). 31P{1H} NMR (δ, CDCl3): 0.8 (Os PPh3).
14: Anal. Calcd for C104H80N2Os2P4 (1862.15): C, 67.08; H, 4.33;
2 H, C H2Cl2), 5.94 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 5.99 (pt, JHH
)
N, 1.50. Found: C, 67.12; H, 4.63; N, 1.83. IR (KBr, cm-1): 2063
1.6 Hz, 1 H, C6H3), 6.03 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.30 (br s, 8
H, C5H4Si), 6.38 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.53 (pt, JHH ) 1.6
Hz, 1 H, C6H3), 6.82 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.99 - 7.14 (m,
20 H, C6H5), 7.25-7.45 (m, 30 H (C6H5) + 2 H (H5/tBu2bpy)), 7.70
- 7.80 (m, 10 H (C6H5) + 1 H (H5′/bpy)), 8.06 (d, 4JH3H5 ) 1.7 Hz,
H3/tBu2bpy), 8.18-8.30 (m, 2 H, H4,H4′/bpy), 8.49-8.67 (m, 4 H,
H3,H3′,H6,H6′/bpy), 8.96 (d, 3JH6H5 ) 6.0 Hz, H6/tBu2bpy). 31P{1H}
1
(s, νCt COs), 2209 (w, νCt Cbpy). H NMR (δ, CDCl3): 4.41 (s, 10 H,
C5H5), 6.93 (d, JHH ) 1.6 Hz, 2 H, C6H3), 7.03-7.17 (m, 40 H,
C6H5), 7.31 (ddd, 3JH5′H4′ ) 7.6 Hz, 3JH5′H6′ ) 4.7 Hz, 4JH5′H3′ ) 1.0
Hz, 1 H, H5′/bpy), 7.38-7.50 (m, 20 H (C6H5) + 1 H (C6H3)), 7.83
3
3
4
(ddd, JH4′H3′ ) 7.9 Hz, JH4′H5′ ) 7.6 Hz, JH4′H6′ ) 1.7 Hz, 1 H,
H4′/bpy), 7.96 (dd, 3JH4H3 ) 8.2 Hz, 4JH4H6 ) 2.2 Hz, 1 H, H4/bpy),
3
5
1
8.42 (dd, JH3H4 ) 8.2 Hz, JH3H6 ) 0.8 Hz, 1 H, H3/bpy), 8.44
NMR (δ, CDCl3): -145.1 (septet, JPF ) 713 Hz, PF6), 0.4 (Os
3
4
5
PPh3), 17.6 (1J
) 2645 Hz, Pt PPh3). MS (ESI-TOF, m/z):
(ddd, JH3′H4′ ) 7.9 Hz, JH3′H5′ ) 1.0 Hz, JH3′H6′ ) 1.0 Hz, 1 H,
31P195Pt
3
4
5
H3′/bpy), 8.70 (ddd, JH6′H5′ ) 4.7 Hz, JH6′H4′ ) 1.7 Hz, JH6′H3′
)
3253.6 [M - PF6]+, 1627.7 [M - PF6]2+, 809.4 [(PPh3)2-
1.0 Hz, 1 H, H6′/bpy), 8.86 (dd, 4JH6H4 ) 2.2 Hz, 5JH6H3 ) 0.8 Hz, 1
H, H6/bpy). 31P{1H} NMR (δ, CDCl3): 0.5 (Os PPh3).
(C5H5)Os(CO)]+.
Synthesis of 1,3-[(Ph3P)2(η5-C5H5)OsCt C]2-5-[(CO)3 ClRe(bpy-
Ct C)]C6H3 (18). To a solution of 20 mg (0.055 mmol) of
[Re(CO)5Cl] (17) in 30 mL of degassed toluene was added 14 (120
mg, 0.064 mmol) in a single portion. The resulting reaction mixture
was heated to 50 °C, and stirring was continued for 5 h at this
temperature, whereby the color of the solution turned from yellow to
dark red and the desired product partly precipitated. After cooling
the reaction solution to ambient temperature the solvent was removed
under vacuum and the remaining residue was subjected to column
chromatography on alumina. Eluting with dichloromethane/toluene
(1:1, v/v) gave an excess of 14. Changing the eluent to acetone/
toluene (1:1, v/v) gave the title complex 18 as a red-brown solid.
Yield: 80 mg (0.037 mmol, 67% based on 17).
Synthesis of trans-[(PPh3)2Pt{1-(FcCt C)-3-[(tBu2bpy)(CO)3-
ReCt C]-5-(Ct C)C6H3}{1-[(Ph3 P)2(η5-C5H5)OsCt C]-3-(bpy-
Ct C)-5-(Ct C)C6H3}] (15). To 50 mg (0.031 mmol) of 1-(FcCt C)-
3-[(tBu2bpy)(CO)3ReCt C]-5-[trans-(Ph3P)2(Cl)PtCt C]C6H3 (1)
and 40 mg (0.037 mmol) of 1-[(Ph3P)2(η5-C5H5)OsCt C]-3-
(bpyCt C)-5-(HCt C)C6H3 (13) dissolved in 10 mL of chloroform
and 10 mL of diethylamine was added 1 mg of [CuI]. The resulting
reaction mixture was stirred for 3.5 h between 30 and 40 °C. After
cooling the mixture to room temperature all volatiles were removed
in an oil-pump vacuum and the residue was purified by column
chromatography on silica gel using a mixture of dichloromethane/
toluene (3:1, v/v) as eluent. Complex 15 was obtained as an orange
powder. Yield: 60 mg (0.022 mmol, 72% based on 1).
Anal. Calcd for C107H80ClN2O3Os2P4Re × 1/2C7H8 (2213.88): C,
59.95; H, 3.82; N, 1.27. Found: C, 59.79; H, 3.79; N, 1.24. IR (KBr,
cm-1): 1894, 1918, 2019 (s, νCO), 2059 (s, νCt COs), 2203 (w,
νCt Cbpy). H NMR (δ, CDCl3): 2.35 (s, 1.5 H, CH3/C7H8), 4.43 (s,
10 H, C5H5), 6.92 (d, JHH ) 1.6 Hz, 2 H, C6H3), 7.04-7.23 (m, 40
Anal. Calcd for C142H111FeN4O3OsP4PtRe (2672.72): C, 63.81; H,
4.19; N, 2.10. Found: C, 63.55; H, 4.29; N, 1.90. IR (KBr, cm-1):
1895, 1905, 2004 (s, νCO), 2065 (m, νCt COs), 2097 (m, νCt CPt), 2212
1
t
(w, νCt CFc). 1H NMR (δ, CDCl3): 1.43 (s, 18 H, Bu), 4.18 (s, 5 H,
C5H5/Fc), 4.19 (pt, JHH ) 1.9 Hz, 2 H, C5H4), 4.37 (s, 5 H,
C5H5/Os), 4.38 (pt, JHH ) 1.9 Hz, 2 H, C5H4), 5.96 (pt, JHH ) 1.6
3
3
H (C6H5) + 2.5 H (C7H8)), 7.32 (ddd, JH5′H4′ ) 7.6 Hz, JH5′H6′
)
4
4.7 Hz, JH5′H3′ ) 1.2 Hz, 1 H, H5′/bpy), 7.40-7.51 (m, 20 H
Hz, 1 H, C6H3), 5.99 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.01 (pt, JHH
)
3
3
(C6H5) + 1 H (C6H3)), 7.90 (ddd, JH4′H3′ ) 8.0 Hz, JH4′H5′ ) 7.6
1.6 Hz, 1 H, C6H3), 6.33 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.55 (pt, JHH
) 1.6 Hz, 1 H, C6H3), 6.80 (pt, JHH ) 1.6 Hz, 1 H, C6H3),
7.00-7.17 (m, 20 H, C6H5), 7.24-7.45 (m, 30 H (C6H5) + 2 H
(H5/tBu2bpy) + 1 H (H5′/bpy)), 7.71 - 7.86 (m, 10 H (C6H5) + 1
Hz, 4JH4′H6′ ) 1.6 Hz, 1 H, H4′/bpy), 7.97-8.07 (m, 3 H, H3,H3′,H4/
3
4
5
bpy), 8.93 (ddd, JH6′H5′ ) 4.7 Hz, JH6′H4′ ) 1.6 Hz, JH6′H3′ ) 1.0
Hz, 1 H, H6′/bpy), 9.13 (dd, 4JH6H4 ) 2.0 Hz, 5JH6H3 ) 0.8 Hz, 1 H,
H6/bpy). 31P{1H} NMR (δ, CDCl3): 0.6 (Os PPh3). MS (ESI-TOF,
m/z): 2169.74 [M + H]+, 809.3 [(PPh3)2(C5H5)Os(CO)]+.
3
4
H (H4′/bpy)), 7.90 (dd, JH4H3 ) 8.4 Hz, JH4H6 ) 2.2 Hz, 1 H,
H4/bpy) 8.05 (d, JH3H5 ) 1.7 Hz, H3/tBu2bpy), 8.41 (dd, JH3H4
)
4
3
8.2 Hz, 5JH3H6 ) 1.0 Hz, 1 H, H3/bpy), 8.43 (ddd, 3JH3′H4′ ) 8.0 Hz,
Modified Synthesis of 1-[(tBu2bpy)(CO)3ReCt C]-3,5-(HCt C)2-
C6H3 (21).9b To a solution of 1,3,5-triethynylbenzene (19) (160 mg,
1.067 mmol) in 30 mL of toluene was added 0.65 mL (1.04 mmol)
of methyllithium (1.6 M in diethyl ether) at -20 °C. This reaction
solution was then allowed to warm to 25 °C and [(tBu2-
bpy)(CO)3ReCl] (20) (200 mg, 0.348 mmol) was added in a single
portion. The resulting reaction mixture was subsequently heated to
reflux under an inert atmosphere of nitrogen for 5 h. After cooling to
25 °C all volatiles were removed under reduced pressure. The
remaining material was subjected to column chromatography on
silica gel using a mixture of diethyl ether/petroleum ether (3:1, v/v)
as the eluent. After removal of the first band, which contained
unreacted 1,3,5-triethynylbenzene, the second band was collected to
give complex 21 as a yellow solid. Yield: 125 mg (0.182 mmol,
4JH3′H5′ ) 1.0 Hz, JH3′H6′ ) 1.0 Hz, 1 H, H3′/bpy), 8.70 (ddd,
5
3JH6′H5′ ) 4.8 Hz, JH6′H4′ ) 1.7 Hz, JH6′H3′ ) 1.0 Hz, 1 H,
4
5
H6′/bpy), 8.80 (dd, 4JH6H4 ) 2.2 Hz, 5JH6H3 ) 1.0 Hz, 1 H, H6/bpy),
8.97 (d, JH6H5 ) 5.8 Hz, H6/tBu2bpy). 31P{1H} NMR (δ, CDCl3):
3
0.4 (Os PPh3), 17.5 (1J
) 2650 Hz, Pt PPh3). MS (ESI-TOF,
31P195Pt
m/z): 2674.1 [M + H]+, 809.4 [(PPh3)2(C5H5)Os(CO)]+.
Synthesis of trans-[(PPh3)2Pt{1-(FcCt C)-3-[(tBu2bpy)(CO)3-
ReCt C]-5-(Ct C)C6H3}{1-[(Ph3P)2(η5-C5H5)OsCt C]-3-[{[Ti](µ-
σ,π-Ct CSiMe3)2}Cu-bpyCt C]-5-(Ct C)C6H3}]PF6 (16). To a
stirred solution of [{[Ti](µ-σ,π-Ct CSiMe3)2}Cu(Nt CMe)]PF6 (6)
(15 mg, 0.019 mmol) in 20 mL of degassed tetrahydrofuran was
added 15 (50 mg, 0.019 mmol) in a single portion. During 2.5 h of
stirring at 25 °C the color of the reaction solution changed from

Unsymmetrical Platinum(II) Bis-acetylide Complexes
Organometallics, Vol. 27, No. 14, 2008 3545
52% based on 20). Please note: The analytical data of 21 cor-
respond to literature Values.9b
for 4 h at 30 °C. Afterward all volatiles were removed in an oil-
pump vacuum and the residue was purified by column chromatog-
raphy on alumina using a mixture of dichloromethane/toluene (5:
1, v/v) as eluent. Complex 27 was obtained as an orange solid.
Yield: 65 mg (0.02 mmol, 63% based on 26).
Synthesis of 1-[(tBu2bpy)(CO)3ReCt C]-3-[(η2-dppf)(η5-C5H5)-
RuCt C]-5-(HCt C)C6H3 (23) and 1-[(tBu2bpy)(CO)3ReCt C]-
3,5-[(η2-dppf)(η5-C5H5)RuCt C]2C6H3 (24). To 220 mg (0.291
mmol) of [(η2-dppf)(η5-C5H5)RuCl] (22) and 200 mg (0.291 mmol)
of 21 dissolved in 25 mL of dichloromethane and 25 mL of
methanol were successively added [NH4]PF6 (55 mg, 0.337 mmol)
and KOtBu (40 mg, 0.357 mmol). The reaction mixture was stirred
for 4 h at ambient temperature. After removal of the solvent under
reduced pressure the residue was purified by column chromatogra-
phy on alumina, eluting with diethyl ether/n-hexane (4:1, v/v). First
unreacted 21 was eluted. The following main fraction contained the
dinuclear complex 23, and finally complex 24 was isolated from the
third band. Compounds 23 and 24 were isolated as orange solids.
Yield: 23, 170 mg (0.121 mmol, 41% based on 21); 24, 155 mg
(0.079 mmol, 25% based on 21).
Anal. Calcd for C171H135FeN4O3OsP6PtReRu (3208.25): C, 64.02;
H, 4.24; N, 1.75. Found: C, 64.52; H, 4.13; N, 1.69. IR (KBr, cm-1):
1894, 1901, 2003 (s, νCO), 2064 (m, νCt COs(Ru)), 2102 (m, νCt CPt),
2210 (w, νCt Cbpy). 1H NMR (δ, CDCl3): 1.39 (s, 18 H, tBu), 3.90 (br
s, 2 H, C5H4), 4.04 (br s, 2 H, C5H4), 4.21 (s, 5 H, C5H5/Ru), 4.23 (br
s, 2 H, C5H4), 4.38 (s, 5 H, C5H5/Os), 5.32 (br s, 2 H, C5H4), 5.70 (pt,
JHH ) 1.6 Hz, 1 H, C6H3), 5.97 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.14
(pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.32 (pt, JHH ) 1.6 Hz, 1 H, C6H3),
6.73 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.81 (pt, JHH ) 1.6 Hz, 1 H,
C6H3), 7.02 - 7.48 (m, 52 H (C6H5) + 2 H (H5/tBu2bpy) + 1 H
(H5′/bpy)), 7.70-7.84 (m, 18 H (C6H5) + 1 H (H4′/bpy)), 7.91 (dd,
4
4
3JH4H3 ) 8.2 Hz, JH4H6 ) 2.2 Hz, 1 H, H4/bpy), 8.06 (d, JH3H5
1.7 Hz, H3/tBu2bpy), 8.42 (dd, 3JH3H4 ) 8.2 Hz, 5JH3H6 ) 0.8 Hz, 1
H, H3/bpy), 8.43 (ddd, 3JH3′H4′ ) 8.0 Hz, 4JH3′H5′ ) 1.0 Hz, 5JH3′H6′
1.0 Hz, 1 H, H3′/bpy), 8.70 (ddd, 3JH6′H5′ ) 4.7 Hz, 4JH6′H4′ ) 1.7 Hz,
5JH6′H3′ ) 1.0 Hz, 1 H, H6′/bpy), 8.81 (dd, 4JH6H4 ) 2.2 Hz, 5JH6H3
)
23: Anal. Calcd for C72H61FeN2O3P2ReRu (1407.35): C, 61.45;
H, 4.37; N, 1.99. Found: C, 61.69; H, 4.72; N, 1.89. IR (KBr,
cm-1): 1895, 2003 (s, νCO), 2062 (m, νCt CRu), 2103 (w, νCt CRe),
)
3307 (m, ν C-H). 1H NMR (δ, CDCl3): 1.46 (s, 18 H, tBu), 2.86 (s,
)
t
0.8 Hz, 1 H, H6/bpy), 9.02 (d, 3JH6H5 ) 6.0 Hz, H6/tBu2bpy). 31P{1H}
1 H, ’C H), 3.94 (dpt, JHP ) 1.2 Hz, JHH ) 2.4 Hz, 2 H, C5H4), 4.17
(br s, 2 H, C5H4), 4.24 (s, 5 H, C5H5), 4.26 (br s, 2 H, C5H4), 5.24
(br s, 2 H, C5H4), 6.55 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.96 (pt, JHH
) 1.6 Hz, 1 H, C6H3), 7.07 (pt, JHH ) 1.6 Hz, 1 H, C6H3),
7.24-7.53 (m, 16 H, C6H5), 7.46 (dd, 3JH5H6 ) 6.0 Hz, 4JH5H3 ) 2.0
NMR (δ, CDCl3): 0.4 (Os PPh3), 17.3 (1J
Pt ) 2659 Hz, PtPPh3),
31P195
54.0 (dppf).
Synthesis of trans-[(PPh3 )2Pt{1-[(tBu2bpy)(CO)3ReCt C]-3-
[(η2-dppf)(η5-C5H5)RuCt C]-5-(Ct C)C6H 3}{1-[(Ph3 P)2(η5-
C5H5)OsCt C]-3-[{[Ti](µ-σ,π-Ct CSiMe3 )2}Cu-bpyCt C]-5-
(Ct C)C6H3}]PF6 (28). To a stirred solution of 27 (45 mg, 0.014
mmol) in 15 mL of degassed tetrahydrofuran was added [{[Ti](µ-
σ,π-Ct CSiMe3)2}Cu(Nt CMe)]PF6 (6) (11 mg, 0.014 mmol) in a
single portion at 25 °C. During the reaction time of 2.5 h a color
change from orange to red was observed. Subsequently, all volatiles
were removed under reduced pressure and the residue was redis-
solved in 2 mL of dichloromethane. Precipitation of the title
complex 28 was achieved by addition of n-hexane (15 mL). The
supernatant solution was removed, and the precipitate was washed
twice with 10 mL portions of diethyl ether. Drying in an oil-pump
vacuum provided complex 28 as an orange-red solid. Yield: 50
mg (0.013 mmol, 91% based on 27).
4
Hz, H5/tBu2bpy), 7.71-7.81 (m, 4 H, C6H5), 8.09 (d, JH3H5 ) 2.0
3
Hz, H3/tBu2bpy), 9.00 (d, JH6H5 ) 6.0 Hz, H6/tBu2bpy). 31P{1H}
NMR (δ, CDCl3): 53.9 (dppf).
24: Anal. Calcd for C111H93Fe2N2O3P4ReRu2 (2126.90): C, 62.68;
H, 4.41; N, 1.32. Found: C, 63.25; H, 4.81; N, 1.23. IR (KBr,
cm-1): 1891, 1902, 2002 (s, νCO), 2065 (m, νCt CRu), 2102 (w,
νCt CRe). 1H NMR (δ, CDCl3): 1.40 (s, 18 H, tBu), 3.89 (dpt, JHP
)
1.2 Hz, JHH ) 2.4 Hz, 4 H, C5H4), 4.07 (br s, 4 H, C5H4), 4.23 (br
s, 4 H, C5H4), 4.25 (s, 10 H, C5H5), 5.43 (br s, 4 H, C5H4), 6.82 (d,
JHH ) 1.6 Hz, 2 H, C6H3), 6.96 (t, JHH ) 1.6 Hz, 1 H, C6H3),
7.12-7.53 (m, 32 H (C6H5) + 2 H (H5/tBu2bpy)), 7.76-7.85 (m,
8 H, C6H5), 8.09 (d, 4JH3H5 ) 1.7 Hz, H3/tBu2bpy), 9.06 (d, 3JH6H5
) 6.0 Hz, H6/tBu2bpy). 31P{1H} NMR (δ, CDCl3): 53.9 (dppf).
Synthesis of 1-[(tBu2bpy)(CO)3ReCt C]-3-[(η2-dppf)(η5-C5H5)-
RuCt C]-5-[trans-(Ph3P)2(Cl)PtCt C]C6H3 (26). To 100 mg (0.071
mmol) of 23 and 70 mg (0.089 mmol) of cis-[(PPh3)2PtCl2] (25)
dissolved in 20 mL of chloroform was added 0.5 mL of diethy-
lamine. The resulting reaction mixture was heated to reflux for 5 h.
After cooling to room temperature and removal of the solvents under
reduced pressure, preparative TLC of the residue (alumina, dichlo-
romethane/toluene, 3:1, v/v) gave a major orange band, from which
complex 26 was obtained as an orange powder. Yield: 90 mg (0.042
mmol, 58% based on 23).
Anal. Calc for C197H179CuF6FeN4O3OsP7PtReRuSi4Ti (3933.61):
C, 60.15; H, 4.59; N, 1.42. Found: C, 59.67; H, 4.69; N, 1.42. IR
(KBr, cm-1): 1899, 2002 (s, νCO), 2062 (m, νCt COs(Ru)), 2101 (m,
1
νCt CPt), 2207 (w, νCt Cbpy). H NMR (δ, CDCl3): -0.45 (s, 18 H,
SiMe3), 0.26 (s, 9 H, SiMe3), 0.29 (s, 9 H, SiMe3), 1.38 (s, 18 H,
tBu), 3.89 (br s, 2 H, C5H4/dppf), 4.01 (br s, 2 H, C5H4/dppf), 4.20 (s,
5 H, C5H5/Ru), 4.23 (br s, 2 H, C5H4/dppf), 4.37 (s, 5 H, C5H5/Os),
5.29 (br s, 2 H, C5H4/dppf), 5.67 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.01
(pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.10 (pt, JHH ) 1.6 Hz, 1 H, C6H3),
6.30 (s, 8 H, C5H4Si), 6.37 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.70 (pt,
JHH ) 1.6 Hz, 1 H, C6H3), 6.81 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.98
- 7.48 (m, 52 H (C6H5) + 2 H (H5/tBu2bpy)), 7.68-7.82 (m, 18 H
Anal. Calcd for C108H90ClFeN2O3P4PtReRu (2162.44): C, 59.99;
H, 4.20; N, 1.30. Found: C, 60.07; H, 4.52; N, 1.23. IR (KBr, cm-1):
1891, 1900, 2002 (s, νCO), 2067 (m, νCt CRu), 2096 (w, νCt CRe), 2119
(w, νCt CPt). 1H NMR (δ, CDCl3): 1.39 (s, 18 H, tBu), 3.89 (dpt, JHP
) 1.2 Hz, JHH ) 2.4 Hz, 2 H, C5H4), 3.99 (br s, 2 H, C5H4), 4.20 (s,
5 H, C5H5), 4.22 (br s, 2 H, C5H4), 5.26 (br s, 2 H, C5H4), 5.49 (pt,
JHH ) 1.6 Hz, 1 H, C6H3), 5.94 (pt, JHH ) 1.6 Hz, 1 H, C6H3), 6.67
(pt, JHH ) 1.6 Hz, 1 H, C6H3), 7.12-7.47 (m, 32 H (C6H5) + 2 H
(H5/tBu2bpy)), 7.67-7.77 (m, 18 H, C6H5), 8.06 (d, 4JH3H5 ) 2.0 Hz,
H3/tBu2bpy), 9.01 (d, 3JH6H5 ) 6.0 Hz, H6/tBu2bpy). 31P{1H} NMR
4
(C6H5) + 1 H (H5′/bpy)), 8.07 (d, JH3H5 ) 1.8 Hz, H3/tBu2bpy),
8.18-8.30 (m, 2 H, H4,H4′/bpy), 8.48-8.67 (m, 4 H, H3,H3′,H6,H6′/
3
bpy), 9.01 (d, JH6H5 ) 5.8 Hz, H6/tBu2bpy). 31P{1H} NMR (δ,
1
CDCl3): -145.1 (septet, JPF ) 713 Hz, PF6), 0.4 (Os PPh3), 17.4
(1J Pt ) 2652 Hz, Pt PPh3), 53.9 (dppf). MS (ESI-TOF, m/z): 3790.2
31P195
[M-PF6]+, 1895.6 [M-PF6]2+, 809.3 [(PPh3)2(C5H5)Os(CO)]+, 749.0
[(dppf)(C5H5)Ru(CO)]+, 579.2 [{[Ti](Ct CSiMe3)2}Cu]+.
Crystal Structure Determinations. Crystal data for 3 and 18
are presented in Table 1. The data for 3 and 18 were collected on
a Oxford Gemini S diffractometer with graphite-monochromatized
Mo KR (λ ) 0.71073 Å, 3) or Cu KR radiation (λ ) 1.54184 Å,
18) at 100(2) K using oil-coated shock-cooled crystals.31 The
(δ, CDCl3): 20.3 (1J
Pt ) 2669 Hz, Pt PPh3), 53.9 (dppf). MS (ESI-
31P195
TOF, m/z): 2164.9 [M + H]+, 749.2 [(dppf)(C5H5)Ru(CO)]+.
Synthesis of trans-[(PPh3 )2Pt{1-[(tBu2bpy)(CO)3ReCt C]-3-
[(η2-dppf)(η5-C5H5)RuCt C]-5-(Ct C)C6H3}{1-[(Ph3P)2(η5-
C5H5)OsCt C]-3-(bpyCt C)-5-(Ct C)C6H3}] (27). To 70 mg
(0.032 mmol) of complex 26 and 45 mg (0.042 mmol) of 13
dissolved in 10 mL of chloroform and 10 mL of diethylamine was
added 1 mg of [CuI]. The resulting reaction mixture was stirred
(31) (a) Kottke, T.; Stalke, D. J. Appl. Crystallogr. 1993, 26, 615. (b)
Kottke, T.; Lagow, R. J.; Stalke, D. J. Appl. Crystallogr. 1996, 29, 465. (c)
Stalke, D. Chem. Soc. ReV. 1998, 27, 171.

3546 Organometallics, Vol. 27, No. 14, 2008
Packheiser et al.
structures were solved by direct methods using SHELXS-9732 or
SIR-9233 and refined by full-matrix least-squares procedures on
F2 using SHELXL-97.34 All non-hydrogen atoms were refined
anisotropically, and a riding model was employed in the refinement
of the hydrogen atom positions.
Acknowledgment. We gratefully acknowledge the gener-
ous financial support coming from the Deutsche Forschungs-
gemeinschaft and the Fonds der Chemischen Industrie.
Supporting Information Available: Tables of atomic coordi-
nates, bond lengths, angles, torsion angles, and anisotropic displace-
ment parameters for 3 and 18. This material is available free of
charge via the Internet at http://pubs.acs.org.
(32) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
(33) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Gualardi, A. J. Appl.
Crystallogr. 1993, 26, 343.
(34) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
Refinement; University of Go¨ttingen, 1997.
OM800232M