An arene-ruthenium(II) complex containing novel hybrid phosphinofluoro ligands

Article abstract of DOI:10.1107/S0108270103005808

In the title compound, (η⁶-p-cymene)[(diphenylphosphinofluorido)trifluoroborato-κ ²P,F][(diphenylphosphinoylfluorido)trifluoroborato-κO]ruthenium (II), [Ru(C₁₂H₁₀BF₁₀OP)(C₁₂H₁₀B F₄P)(C₁₀H₁₄)], the hybrid Ph2PFBF3 ligand is bidentate (κ²P, F) and thus forms a five-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 Ru-O, Ru-F and Ru-P bond lengths are 2.107 (3), 2.135 (4) and 2.3145 (15) A, respectively.

Full text of DOI:10.1107/S0108270103005808

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

metal-organic compounds
product (Ph2PFBF3). Spectroscopic analysis, 1H NMR (CDCl3,
p.p.m.): ꢅ 7.12±7.75 (m, Ph); 31P{1H} NMR (CDCl3, p.p.m.): ꢅ 76.5;
19F NMR (CDCl3, p.p.m.): ꢅ 187.2 (d, J = 118 Hz, PFB), 319.3
(BF3); MS (EI): m/z 273 (M+ + 1); IR (Nujol, cm 1): ꢆ (BÐF) 1154
(s), 901 (s), 856 (s) and 712 (m). Ph2PFBF3 was dissolved in CH2Cl2,
®ve-membered chelate ring with a bite angle of 78.48 (12)ꢀ,
which is more acute than that found for the bidentate
Me2PCHCHPMe2 phosphine ligand in RuII complexes (Field
et al., 1994). The RuÐC(ring) distances are in the range
Ê
2.158 (5)±2.245 (7) A and agree well with those found in other
(p-cymene)ruthenium(II) complexes, for example, [(p-cy-
1
affording Ph2P(O)FBF3. Spectroscopic analysis, H NMR (CDCl3,
p.p.m.): ꢅ 7.09±7.77 (m, Ph); 31P{1H} NMR (CDCl3, p.p.m.): ꢅ 84.1; 19
F
Ê
mene)RuCl(Me2PCH2CH2SMe)](BPh4) [2.198 (5)±2.267 (6) A;
Suzuki et al., 1996] and [(p-cymene)RuCl2(PH2Cy)] [2.175 (4)±
NMR (CDCl3, p.p.m.): ꢅ 164.6 (d, J = 96 Hz, PFB), 302.7 (BF3);
MS (EI): m/z 288 (M+); IR (Nujol, cm 1): ꢆ(BÐF) 1148 (s), 892 (s),
843 (s) and 716 (m); ꢆ(P O) 1016 (vs).
Ê
Â
2.238 (5) A; Van der Maelen Urõa et al., 1994]. Note that the
longest RuÐC bond (Ru1ÐC6; see Table 1) is trans with
respect to the P atom, as a result of the strong trans in¯uence
of the PPh2 group. The RuÐO bond length in (I) indicates
considerable single-bond character. The RuÐF bond length in
(I) is comparable to those in cis-[Ru(dmpe)2F(FÁ Á ÁHF)]
For the synthesis of (I), Ph2PFBF3 (272 mg, 1.0 mmol) was
dissolved in CH2Cl2 (5 ml) and the solution was added to a ¯ask
containing a solution of [(p-cymene)Ru(acetone)3](BF4) (248 mg,
0.5 mmol) in CH2Cl2 (5 ml). The resulting solution was stirred for 2 h
and the solvent removed in vacuo. Hexane (20 ml) was added to the
¯ask to give an orange precipitate. Recrystallization from CH2Cl2/
hexane afforded orange prismatic crystals.
Ê
[2.101 (3) and 2.168 (3) A; Kirkham et al., 2001]. The RuÐP
bond distance is normal and also agrees well with those in
Â
related complexes (Suzuki et al., 1996; Van der Maelen Urõa et
al., 1994).
The P2ÐF5 bond length of the coordinated chelate ligand is
slightly longer than the P1ÐF1 bond length of the terminal
coordination ligand (Table 1). There are three types of BÐF
Crystal data
3
[Ru(C12H10BF4OP)-
(C12H10BF4P)(C10H14)]
Mr = 795.24
Dx = 1.550 Mg m
Mo Kꢈ radiation
Cell parameters from 3433
re¯ections
Monoclinic, Cc
a = 17.7179 (13) A
ꢉ = 2.2±25.6ꢀ
ꢄ = 0.63 mm
T = 294 (2) K
Ê
Ê
bond in (I), viz. BÐꢄ-F(P) bonds [B2ÐF5 = 1.485 (8) A and
1
Ê
b = 11.2784 (8) A
Ê
B1ÐF1 = 1.472 (8) A], the BÐꢄ-F(Ru) bond [B2Ð
Ê
c = 18.4455 (13) A
ꢇ = 112.410 (2)ꢀ
Prism, orange
0.22 Â 0.18 Â 0.15 mm
Ê
F6 = 1.452 (8) A] and terminal BÐF bonds [1.344 (9)±
3
Ê
V = 3407.6 (4) A
Z = 4
Ê
1.399 (8) A]. On the other hand, the B2ÐF5ÐP2 angle is
smaller than both the B1ÐF1ÐP1 angle (Table 1) and that in
the reported complex [Mo(ꢀ5-C9H7)(CO)2{P-ꢀ3-(tBu)CPC-
(tBu)PFBF3}] [131.1 (6)ꢀ; Hitchcock et al., 1994]. Thus, it is
reasonable to say that the coordination of the Ru atom by the
Ph2PFBF3 chelate ligand results in the elongation of the PÐF
and BÐꢄ-F(P) bonds and the reduction of the BÐFÐP angle
(Barthazy et al., 2000). Angles involving P atoms re¯ect a
tetrahedral geometry, and it is also noteworthy that the
RuÐPÐC and OÐPÐF angles are larger than the FÐPÐC
angles.
Data collection
Bruker SMART APEX CCD
diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.294, Tmax = 0.401
10 808 measured re¯ections
6382 independent re¯ections
5757 re¯ections with I > 2ꢂ(I)
Rint = 0.028
ꢉmax = 26.0ꢀ
h = 21 ! 21
k = 11 ! 13
l = 22 ! 22
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
Experimental
Ru1ÐP2
Ru1ÐF6
Ru1ÐO1
Ru1ÐC2
Ru1ÐC3
Ru1ÐC4
2.3145 (15)
2.135 (4)
2.107 (3)
2.189 (6)
2.159 (5)
2.159 (5)
Ru1ÐC5
Ru1ÐC6
Ru1ÐC7
P1ÐF1
P2ÐF5
P1ÐO1
2.186 (5)
2.245 (6)
2.220 (5)
1.554 (4)
1.581 (4)
1.478 (4)
Treatment of Ph2PCl in dry CH2Cl2 with an equivalent amount of
Ag(BF4) resulted in a light yellow solution with a white precipitate
P2ÐRu1ÐF6
P2ÐRu1ÐO1
P2ÐRu1ÐC2
P2ÐRu1ÐC3
P2ÐRu1ÐC4
P2ÐRu1ÐC5
P2ÐRu1ÐC6
P2ÐRu1ÐC7
O1ÐRu1ÐC2
F6ÐRu1ÐO1
F6ÐRu1ÐC2
F6ÐRu1ÐC3
F6ÐRu1ÐC4
F6ÐRu1ÐC5
F6ÐRu1ÐC6
F6ÐRu1ÐC7
O1ÐRu1ÐC3
O1ÐRu1ÐC4
O1ÐRu1ÐC5
78.48 (12)
84.93 (11)
117.3 (2)
93.74 (16)
96.71 (16)
123.63 (15)
160.86 (18)
154.51 (18)
97.8 (2)
81.78 (15)
164.1 (2)
148.8 (2)
112.55 (18)
90.82 (19)
98.8 (2)
O1ÐRu1ÐC6
O1ÐRu1ÐC7
F1ÐP1ÐO1
113.6 (2)
93.68 (18)
115.5 (2)
103.9 (2)
109.4 (3)
110.1 (3)
108.4 (3)
109.3 (3)
106.39 (16)
115.38 (17)
118.74 (17)
105.6 (2)
104.2 (2)
105.3 (2)
147.6 (3)
134.7 (4)
120.2 (4)
121.5 (3)
F1ÐP1ÐC11
F1ÐP1ÐC17
O1ÐP1ÐC11
O1ÐP1ÐC17
C11ÐP1ÐC17
Ru1ÐP2ÐF5
Ru1ÐP2ÐC23
Ru1ÐP2ÐC29
F5ÐP2ÐC23
F5ÐP2ÐC29
C23ÐP2ÐC29
Ru1ÐO1ÐP1
P1ÐF1ÐB1
126.6 (2)
128.1 (2)
165.64 (19)
148.56 (19)
P2ÐF5ÐB2
Ru1ÐF6ÐB2
(see Scheme above). The solution was ®ltered to remove the AgCl
precipitate and the solvent was pumped off to give a yellow oily
ꢁ
Acta Cryst. (2003). C59, m156±m158
Yao, Liu and Zhang
[Ru(C12H10BF4OP)(C12H10BF4P)(C10H14)] m157

metal-organic compounds
Re®nement
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Re®nement on F2
R[F2 > 2ꢂ(F2)] = 0.043
wR(F2) = 0.098
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6382 re¯ections
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(Á/ꢂ)max < 0.001
3
Ê
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Ê
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ꢁ
m158 Yao, Liu and Zhang [Ru(C12H10BF4OP)(C12H10BF4P)(C10H14)]
Acta Cryst. (2003). C59, m156±m158