2013. 54, 2
– . 408 – 410
UDC 548.73:547.13:546.93
CRYSTAL STRUCTURE
OF (K5-PENTAMETHYLCYCLOPENTADIENYL){BIS(PENTAFLUOROPHENYL)THIOMETHYLPHENYL
PHOSPHINE-N2S,P )CHLOROIRIDIUM(III) TETRAFLUOROBORATE
R.M. Bellabarba1,2, M. Nieuwenhuyzen1, G.C. Saunders3
1
The School of Chemistry, Queencs University Belfast, David Keir Building, Belfast, BT9 5BA, United Kingdom
Current address: Sasol Technology (UK) Ltd, Purdie Building, North Haugh, St Andrews, KY16 9ST, United
Kingdom
3
Department of Chemistry, The University of Waikato, Private Bag 3105, Hamilton 3240, New Zealand
E-mail: g.saunders@waikato.ac.nz
2
Received November, 9, 2011
Revised — January, 31, 2012
The salt (K5-pentamethylcyclopentadienyl){bis(pentafluorophenyl)thiomethylphenylphosphineN2S,P )chloroiridium(III) tetrafluoroborate, [(K5-C5Me5)IrCl{N2S,P -(C6F5)2PC6H4SMe-2}]BF4,
crystallizes as a conglomerate in the orthorhombic crystal system in space group P212121 with
unit cell parameters a = 9.9621(9) Å, b = 16.7793(15) Å, c = 18.5040(16) Å, V = 3093.1(5) Å3,
Z = 4, dcalc = 2.014 g cm–3 <...>
K e y w o r d s: conglomerate, K5-pentamethylcyclopentadienyl, iridium, X-ray structure <...>
Intramolecular dehydrofluorinative coupling of pentamethylcyclopentadienyl and phosphines
bearing polyfluoroaryl substituents occurs readily in cationic complexes of rhodium [ 1, 2 ] and iridium [ 2, 3 ], especially in cases where the phosphine moiety is a component of a chelating ligand <...> ]. Here we report the
structure of an iridium complex, [(K5-C5Me5)IrCl{NP,NS-(C6F5)2PC6H4SMe-2}]BF4 (1), which undergoes intramolecular dehydrofluorinative coupling [ 3 ], and which also crystallizes as a conglomera <...> l. Crystals of compound 1 [ 3 ] were grown from dichlorometha <...> e. Diffraction data
of a single crystal were collected at 153(2) K on a Bruker SMART diffractometer using the SAINT-NT
[ 6 ] software with graphite-monochromated MoKD radiati <...> n. Crystallographic and refinement data are
given in Table <...> d. Empirical absorption corrections
were applied using SADABS [ 8 <...> ]. The structure was solved using direct methods and refined with the
programme package SHELXTL [ 9 <...> ]. The non-hydrogen atoms were refined with anisotropic thermal
paramete <...> s. Hydrogen atom positions were added, and idealized positi <...>
CRYSTAL_STRUCTURE_OF(-PENTAMETHYLCYCLOPENTADIENYL){BIS(PENTAFLUOROPHENYL)TIOMETHYLPHENYLPHOSPHINE-K2S,P)CHLOROIRIDIUM(III)TETRAFLUOROBORATE.pdf
2013. 54, 2
-
– -
UDC 548.73:547.13:546.93
CRYSTAL STRUCTURE
OF (u5-PENTAMETHYLCYCLOPENTADIENYL){BIS(PENTAFLUOROPHENYL)THIOMETHYLPHENYL
PHOSPHINE-x2S,P)CHLOROIRIDIUM(III) TETRAFLUOROBORATE
R.M. Bellabarba1,2 , M. Nieuwenhuyz e n 1, G.C. Saunders3
1The School of Chemistry, Queens University Belfast, David Keir Building, Belfast, BT9 5BA, United Kingdom
2Current address: Sasol Technology (UK) Ltd, Purdie Building, North Haugh, St Andrews, KY16 9ST, United
Kingdom
3Department of Chemistry, The University of Waikato, Private Bag 3105, Hamilton 3240, New Zealand
E-mail: g.saunders@waikato.ac.nz
Received November, 9, 2011
Revised — January, 31, 2012
The salt (u5-pentamethylcyclopentadienyl){bis(pentafluorophenyl)thiomethylphenylphosphinex2S,P)chloroiridium(III)
tetrafluoroborate, [(u5-C5Me5)IrCl{x2S,P-(C6F5)2PC6H4SMe-2}]BF4,
crystallizes as a conglomerate in the orthorhombic crystal system in space group P212121 with
unit cell parameters a = 9.9621(9) Å, b = 16.7793(15) Å, c = 18.5040(16) Å, V = 3093.1(5) Å3,
Z = 4, dcalc = 2.014 gcm–3. The structure of the SIr, SS stereoisomer reveals three-legged piano
stool geometry about Ir, with Cp*—Ir, Ir—P, Ir—S and Ir—Cl distances of 1.847(5),
2.2791(14), 2.3451(13) and 2.3840(12) Е respectively.
Keywords: conglomerate, u5-pentamethylcyclopentadienyl, iridium, X-ray structure.
Intramolecular dehydrofluorinative coupling of pentamethylcyclopentadienyl and phosphines
bearing polyfluoroaryl substituents occurs readily in cationic complexes of rhodium [ 1, 2 ] and iridium
[ 2, 3 ], especially in cases where the phosphine moiety is a component of a chelating ligand.
A number of the products are chiral, with some crystallizing as conglomerates, for example the salts
comprising cations of tethered ligands [{u5,xP,xP-C5Me4CH2-2-C5F3N-4-P(C6F5)CH2CH2PPh2}
RhCl][BF4] [ 4 ] and [{u5,xP-C5Me4CH2-2-C6F4P(C6F5)CH2P(C6F5)2}RhCl2] [ 5 ]. Here we report the
structure of an iridium complex, [(u5-C5Me5)IrCl{xP,xS-(C6F5)2PC6H4SMe-2}]BF4 (1), which undergoes
intramolecular dehydrofluorinative coupling [ 3 ], and which also crystallizes as a conglomerate.
Experimental. Crystals of compound 1 [ 3 ] were grown from dichloromethane. Diffraction data
of a single crystal were collected at 153(2) K on a Bruker SMART diffractometer using the SAINT-NT
[ 6 ] software with graphite-monochromated MoKh radiation. Crystallographic and refinement data are
given in Table 1. Lorentz and polarization corrections were applied. Empirical absorption corrections
were applied using SADABS [ 8 ]. The structure was solved using direct methods and refined with the
programme package SHELXTL [ 9 ]. The non-hydrogen atoms were refined with anisotropic thermal
parameters. Hydrogen atom positions were added, and idealized positions and a riding model with
fixed thermal parameters (Uij) 1.2Ueq for the atom to which they are bonded (1.5 for CH3)) were used
for subsequent refinements. The function minimized was [w(|F0|2 – |Fc|2)]. CCDC 221314 contains
the supplementary crystallographic data for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting
The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336033.
© Bellabarba R.M., Nieuwenhuyzen M., Saunders G.C., 2013
. 408 – 410
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