metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Ph2PCl and Ag(BF4) in order to isolate the hybrid phosphi-
no¯uoro Ph2PFBF3 ligand with one PÐF bond (see reaction
Scheme in Experimental). In order to reveal the coordination
modes of this ligand in ruthenium complexes, we prepared the
title complex, (I), and carried out a diffraction analysis. In this
paper, we report our initial ®ndings on the structure of (I). To
our knowledge, this is the ®rst structural example of a tran-
sition metal complex containing the hybrid Ph2PFBF3 ligand.
ISSN 0108-2701
An arene±ruthenium(II) complex
containing novel hybrid phosphino-
fluoro ligands
Wen-Rui Yao, Ze-Hua Liu and Qian-Feng Zhang*
Department of Chemistry and Chemical Engineering, Anhui University of
Technology, Maanshan, Anhui 243002, People's Republic of China
Correspondence e-mail: zhangqf@ahut.edu.cn
Received 20 February 2003
Accepted 12 March 2003
Online 31 March 2003
In the title compound, (ꢀ6-p-cymene)[(diphenylphosphino-
¯uorido)tri¯uoroborato-ꢁ2P,F][(diphenylphosphinoyl¯uor-
ido)tri¯uoroborato-ꢁO]ruthenium(II), [Ru(C12H10BF4OP)-
(C12H10BF4P)(C10H14)], the hybrid Ph2PFBF3 ligand is
bidentate (ꢁ2P,F) and thus forms a ®ve-membered chelate
ring. The Ph2PFBF3 ligand is unusually ligated to the metal
through the P atom of the PPh2 moiety and through one of the
F atoms of the BF4 moiety. The phosphine-oxidized Ph2P(O)-
FBF3 ligand is bonded to the Ru atom via the O atom. The Ru
centre has a pseudo-octahedral coordination environment, in
which the phenyl ring occupies three of the corners of the
distorted octahedron. The RuÐO, RuÐF and RuÐP bond
In the neutral complex (I), the Ru atom exhibits a distorted
octahedral coordination sphere, with the phenyl ring of the
p-cymene ligand formally occupying three octahedral sites.
The structure of (I) is depicted in Fig. 1. The O atom of
Ph2P(O)FBF3 and the bidentate Ph2PFBF3 ligand, which is
bonded to the metal centre via the P and an F atom, complete
the coordination sphere, which may infer that the Ru atom
exhibits a chiral centre. The hybrid Ph2PFBF3 ligand is
unusually ligated to the metal through the P atom of the PPh2
moiety and through one of the Fatoms of the BF4 moiety. This
novel coordination mode is the ®rst example of a ruthenium
complex system. Ph2PFBF3 acts as a bidentate ligand to form a
Ê
lengths are 2.107 (3), 2.135 (4) and 2.3145 (15) A, respectively.
Comment
The chemistry of half-sandwich (ꢀ6-arene)ruthenium(II) com-
plexes is currently of much interest because of the numerous
applications of new catalytic systems for a variety of organic
transformation reactions (Noyori, 1994). Ruthenium-based
catalytic systems are effective in the hydrogenation of
ketones for the synthesis of chiral alcohols (Bernard et al.,
2000). Studies by Noyori and co-workers have shown that the
transfer hydrogenation of prochiral ketones can be achieved
in high enantiomeric excess by tailoring chiral ruthenium
catalysts; accordingly, investigations of chiral ruthenium
catalysts are now common (Yamakawa et al., 2000). As part of
our research on ruthenium complexes with S- and Se-donor
ligands, we are interested in preparing some new bulk ligands
by the hybridization of different atoms (Zhang et al., 2002).
The most intriguing properties of alkylphosphine ligands are
related to the strong ꢂ-donor P atom and electron-donating
alkyl groups, which can stabilize the 16e ruthenium species to
convert to their 18e congeners by oxidative addition at the
metal centre (Halpern, 1970). Tetra¯uoroborate as a ligand in
reactive complexes can be easily replaced by ꢃ- and ꢂ-donors,
suggesting that tetra¯uoroborate is a very good leaving group
(Appel & Beck, 1985). Thus, we attempted the reaction of
Figure 1
A perspective view of (I). H atoms have been omitted for clarity and
displacement ellipsoids are drawn at the 50% probability level.
m156 # 2003 International Union of Crystallography
DOI: 10.1107/S0108270103005808
Acta Cryst. (2003). C59, m156±m158
Yao, Wen-Rui
