Synthesis and characterization of some arene hydrido-complexes 6-arene)(EPh3)2H>+ (η6-arene = benzene, p-cymene or hexamethylbenzene; E = P, As or Sb). Crystal structure of 6-C6H6)(PPh3)2H>BF4

Article abstract of DOI:10.1016/S0022-328X(97)00707-9

<(Ru(η⁶-arene)Cl2)2> (η⁶-arene = benzene, p-cymene or hexamethylbenzene) reacts with EPh3 (E = P, As or Sb) in methanol to give monomeric cationic arene hydrido complexes 6-arene)(EPh3)2H>⁺ in presence of AgBF4 or AgPF6.However, reactions in presence of triphenylphosphine also yield a symmetrically bridged tris (μ-methoxy) complex <(PPh3)3Ru(μ-OMe)3Ru(PPh3)3>⁺.The crystal structure of 6-C6H6)(PPh3)2H>BF4 has been determined.Crystal data, monoclinic system, space group P2_1/n, a=14.792 (2) Angstroem; b=14.351 (1) Angstroem; c=17.661 (2) Angstroem; β=102.25 (1) deg and Z=4.Crystal structure determination reveals the distortion of the Ru(PPh3)2H⁺ unit in the cation 6-C6H6)(PPh3)2H>⁺. - Keywords: Arene hydrido complexes; Ruthenium; Phosphine; Arsine; Stibine

Full text of DOI:10.1016/S0022-328X(97)00707-9

Journal of Organometallic Chemistry 560 (1998) 35–40
Synthesis and characterization of some arene hydrido-complexes
[Ru(p6-arene)(EPh3)2H]+ (p6-arene=benzene, p-cymene or
hexamethylbenzene; E=P, As or Sb). Crystal structure of
[Ru(p6-C6H6)(PPh3)2H]BF4
Om Singh Sisodia a, A.N. Sahay a, D.S. Pandey a,*, U.C. Agarwala b, N.K. Jha c,
Pankaj Sharma d, A. Toscano d, A. Cabrera d
a Department of Chemistry, APS Uni6ersity, Rewa-486003 (MP), India
b Department of Chemistry, Indian Institute of Technology, Kanpur-208016, India
c Department of Chemistry, Indian Institute of Technology, Delhi-110016, India
d Instituto de Quimica, UNAM, Deleq, Coyoacan, Mexico DF 04510, Mexico
Received 28 July 1997; received in revised form 29 October 1997
Abstract
[{Ru(p6-arene)Cl2}2] (p6-arene=benzene, p-cymene or hexamethylbenzene) reacts with EPh3 (E=P, As or Sb) in methanol to
give monomeric cationic arene hydrido complexes [Ru(p6-arene)(EPh3)2H]+ in presence of AgBF4 or AgPF6. However, reactions
in presence of triphenylphosphine also yield a symmetrically bridged tris (v-methoxy) complex [(PPh3)3Ru(v-OMe)3Ru(PPh3)3]+
The crystal structure of [Ru(p6-C6H6)(PPh3)2H]BF4 has been determined. Crystal data, monolinic system, space group P21/n
a=14.792 (2) A; b=14.351 (1) A; c=17.661 (2) A; i=102.25 (1)° and Z=4. Crystal structure determination reveals the
distortion of the Ru(PPh3)2H+ unit in the cation [Ru(p6-C6H6)(PPh3)2H]+. © 1998 Elsevier Science S.A. All rights reserved.
.
,
˚
˚
˚
Keywords: Arene hydrido complexes; Ruthenium; Phosphine; Arsine; Stibine
1. Introduction
evaluation of catalytic potential towards olefin hydro-
genation, of the arene hydrido complexes, has been the
subject of several previous publications ([4]a–i). Prepa-
ration of arene hydrido ruthenium complexes from
reactions of [{Ru(p6-arene)Cl2}]2 with 1M Na2CO3 in
propanol or from reaction of H2 (4 atm) in
dichloromethane containing triethylamine or by using
reducing agents like LiAlH4 or NaBH4 in tetrahydro-
furan is well documented ([4]a,b). Preparation of
monomeric arene hydrido complexes with the formula-
tions [MHX(p6-arene)L] (M=Ru, Os: X=C1−,
CF3COO−) in methanol in presence of Zn dust is also
reported ([4]c, [5]). Because of our interest in the ruthe-
nium (II) arene complexes and as a prelude to our
detailed investigations towards the synthesis of hydrido
complexes and evaluation of their catalytic activities,
A series of dinuclear mono-, bis- and tris- (v-hy-
drido) complexes derived from [{M(C5Me5)Cl2}2] (M=
Rh, Ir) having additional bridging ligands viz. halide,
acetate or trifluoroacetate groups are very active ho-
mogenous catalysts for olefin hydrogenation [1]. In this
regard, isoelectronic arene ruthenium complexes
[{Ru(p6-arene)Cl2}2] (arene=benzene and it’s deriva-
tives) have also drawn special attention ([2]a,d). It has
been known for some time, that in olefin hydrogenation
reactions, involving arene ruthenium complexes, arene
hydrido complexes, serve as the key intermediates
([3]a,b). Therefore, the synthesis, characterization and
* Corresponding author.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(97)00707-9

36
O. Singh Sisodia et al. / Journal of Organometallic Chemistry 560 (1998) 35–40
we have examined the reactivity of [{Ru(p6-arene)Cl2}2]
(p6-arene=benzene, p-cymene or hexamethylbenzene)
in methanol in the presence of AgBF4 or AgPF6 with
EPh3 (E=P, As or Sb). We observed that the reaction
resulted in the formation of cationic monomeric arene
hydrido complexes [Ru(p6-arene)(EPh3)2H]+. However
in such a reaction involving triphenylphosphine, we
could also isolate a tris (v-methoxy) complex with the
formulation [(PPh3)3Ru(v-OMe)3Ru(PPh3)3]+. In this
communication, we describe simple, convenient single
step reproducible syntheses of some monomeric,
cationic, arene hydrido ruthenium complexes under
very mild reaction conditions. We also describe herein,
the single crystal X-ray structure of one of such hydrido
complexes [Ru(p6-C6H6)(PPh3)2H]BF4.
region 1200–950 and 600–300 cm−1, assignable to
methoxy vibrations [10]. However, the characteristic
bands due to triphenylphosphine and counter anion
PF6 also appear in the same region, hence unambiguous
assignments cannot be made. But, presence of methoxy
1
group in the complex is evident by H NMR signal of
the methoxy group in the NMR spectra of the complex.
1
The H NMR spectra of the complex (1a, 2a, 3a)
displayed triplets in the region d −9.0 to −10.0 ppm,
whereas complex (1b, 1c, 2b, 2c, 3b, 3c) displayed sharp
singlets in the region l −8.92 to −11.5 ppm,
assignable to metal-bound hydride (Ru–H). The triplet
present in the high field side with JH-P=32–37.2 Hz in
1
the H NMR spectra of (1a, 2a, 3a) suggest that the
hydride ligand is coupled with two equivalent phos-
phine ligands [11]. It is interesting to note that the
chemical shifts of the Ru–H resonance in these com-
plexes is dependent upon the nature of p6-arene. This
observation is in keeping with the conclusions drawn
from IR spectral studies. The 1H NMR spectra of
complex (4) exhibited a sharp singlet at l 3.12 ppm and
a broad multiplet in the region l 7.03–7.70 ppm. The
singlet at l 3.12 ppm is assigned to methoxy protons
and the broad multiplet at l 7.03–7.70 ppm as to the
aromatic protons of triphenylphosphine ligand. The
presence of a sharp singlet corresponding to methoxy
group suggests that all these protons are chemically
equivalent and it is only possible if the methoxy groups
form a symmetrical bridge between the two Ru(II)
centers.
FAB mass spectra of the complex (1a) displayed a
peak corresponding to molecular ion [Ru(p6-
arene)H(PPh3)2]+ at m/z 705. Fragmentation pattern
indicated that the molecular ion looses the hydride
ligand in the next step to form [Ru(p6-C6H6)(PPh3)2]2+
ion, the corresponding peak is present at m/z 704 in the
spectra. This ion in the next step loses the p6-C6H6 to
give [Ru(PPh3)2]2+, which is evident from the presence
of basal peak at m/z 625. This step ligand suggests that
the [Ru(PPh3)2]2+ moiety is more stable as compared
to [Ru(p6-C6H6)(PPh3)]2+. The overall fragmentation
pattern for this molecule may be given as:
2. Results and discussion
Pale yellow to golden yellow crystalline complexes
resulting from the reaction of [{Ru(p6-arene)Cl2}]2
(arene=benzene, p-cymene or hexa methylbenzene)
with EPh3 in presence of AgBF4 or AgPF6 with the
formulation [Ru(p6-arene)(EPh3)2H]+ are air stable
solids soluble in acetone, acetonitrile, nitromethane,
dimethylformamide and dimethyl sulfoxide, partially
soluble in methanol, dichloromethane, chloroform, in-
soluble in benzene, petroleum ether and diethylether.
However, the tris (v-methoxy) complex is insoluble in
most of the common organic solvents. These complexes
gave conducting solution in nitromethane with charac-
teristic values of 1:1 electrolyte.
The infrared spectra of the complex (1a–1c, 2a–2c
and 3a–3c) displayed sharp strong bands in the region
1995–2025 cm−1 along with the characteristic bands
due to p6-arene, EPh3 and counter anions BF4 or PF6.
The band in the region (1995–2025 cm−1) has been
assigned to w(Ru–H). It is interesting to note that, the
position of w(Ru–H) band is dependent on the nature
of p6-arene, present in the complex viz. this band shifts
towards higher wave number side as one moves from
the benzene complex to hexamethylbenzene complex.
Thus, it appears that the position of w(Ru–H) is sensi-
tive to methyl substitution on the arene ring. Infrared
spectra of the complex (4) exhibited strong band in the
The above pattern supports well our formulation for
the complex. The molecular ion peaks in the corre-
sponding p-cymene and hexamethylbenzene complexes

O. Singh Sisodia et al. / Journal of Organometallic Chemistry 560 (1998) 35–40
37
exhibited a slippage away from idealized p6-position
(Fig. 1). The arene ring is planar with average Ru–C
˚
distances of 2.273(12) A [range 2.243(17)–2.353(15)
˚
˚
A]. The metal center Ru lies 1.8112 A from the arene
ring plane, which is longer than the average ruthe-
nium arene ring distances in other Ru(II)–arene com-
plexes [13]. The C–C distances within the benzene
˚
ring are comparable [average 1.403(30) A, range
1.298(34)–1.482(37) A].
˚
The Ru–P(1) and Ru–P(2) distances are 2.329(2)
˚
and 2.327(2) A, respectively and these are comparable
with Ru–P distances in closely related system like
[Ru(p6-arene)H(PPh3)2]+ (p6-arene=toluene), [RuH-
(PPh3)2(nPh-PPh2)]+ and [Ru(PPh3)2(Pys)2] ([7]d,e)
The P(1)–Ru–P(2) angle in the complex is 97.2(1)°
which is comparable to the one reported in
[Ru(PPh3)2H(nPh-PPh2]+ where the P(1)–Ru–H and
P(2)–Ru–H angles are 85.1(31) and 76.6(27)°, respec-
tively. These indicate that the hydride hydrogen is not
symmetrically placed with respect to two metal
bonded phosphorus atoms. The Ru–H distance in the
Fig. 1. ORTEP drawing of cation [Ru(p6-C6H6)(PPh3)2H]+
.
(2a and 3a) appeared at m/z 761 and 789, respec-
tively. However, it was observed that fragmentation
pattern for these complexes are different in step II, as
compared to that for complex (1a). Interestingly, the
fragmentation pattern for (2a) and (3a) in step II
involves loss of a PPh3 ligand rather than p6-arene,
as indicated by presence of peaks at m/z 498 and
525, respectively. This, clearly suggests that for p-
cymene and hexamethylbenzene complexes, [Ru(p6-
arene)(PPh3)]2+ moiety is more stable as compared to
[Ru(PPh3)2]2+, it may be due to the effect of methyl
substitution on the arene rings [12].
˚
cation is 1.62(9) A, which is comparable to the Ru–
H
distances in an analogous complex [Ru(p6-
arene)(PPh3)2H]+ (p6-arene=toluene) ([4]f). However
it is a longer than the Ru–H bond lengths in
[RuH(p5-C5H5)(PMe3)2] and [RuH(C6H6)(dippe)]+
([4]i).
The crystal structure determination confirms the
distortion of [RuH(PPh3)2]+ unit in the cation and
supports well the molecular orbital calculations at the
extended huckel level to explore the structural distor-
tion in such systems by Siedle et al. ([4]f).
The cation in the molecule adopted a distorted ‘pi-
ano stool’ structure in which the [RuH(PPh3)2]2+ unit
3. Experimental
Table 1
Summary of data for the crystal structure analysis of [Ru(p6-
C6H6)(PPh3)2H]BF4
All the synthetic operations were performed under
oxygen free nitrogen atmosphere. The solvents were
dried and distilled before use. h-Phellandrene,
triphenylphosphine, triphenylarsine, triphenylstibine
(all Fluka) hydrated ruthenium (III) chloride, cyclo-
hexa-1,3-diene, silver tetrafluoroborate and silver hex-
afluorophosphate (all Aldrich) were used as received.
The complexes [Ru(p6-C6H6)Cl2}2] [6], [{Ru(p6-
C10H14)Cl2}2] [7] and [Ru(p6-C6Me6)Cl2}2] [7] were
prepared following the literature procedures.
Elemental analyses in the complexes were per-
formed by the microanalytical laboratory of RSIC,
Central Drug Research Institute, Lucknow. Infrared
spectra were recorded on a Perkin Elmer 577 Spec-
trophotometer. NMR spectra were taken on a Bruker
WM-400 and Bruker DRX-300MHZ spectrometers
with tetramethylsilane as the internal standard. FAB
mass spectra were obtained on a JEOL SX-120 A
mass spectrometer with NBA as the matrix.
Formula
C42H37BF4P2Ru
791.5
Formula weight
Color, habbit.
Crystal system
Space group
Yellow, prism
Monoclinic
P21/n
˚
˚
Unit cell dimensions
a=14.792(2) A
b=14.351(1) A
˚
c=17.66 (2) A
i=102.25(1)°
3
˚
Volume
3663.8(7) A
Z
4
Density calculated
Absorption coefficient
F(000)
1.435 mg m−3
0.565 mm−1
1616
Reflections collected
Independent reflections
Observed reflections
R; Rꢀ
8744
8424 (R(int)=0.506%)
4818 (F\4.0| (F))
0.0589; 0.0663
1.09
GOF

38
O. Singh Sisodia et al. / Journal of Organometallic Chemistry 560 (1998) 35–40
Table 2 (continued)
Table 2
Positional parameters and U(eq) for [Ru(p6-C6H6)(PPh3)2H]BF4.
(atomic coordinates (×104) and equivalent isotropic displacement
2
3
Atom
x
y
z
U(eq)a (A ×10 )
˚
coefficients (A ×10 ) for [(Ph3P)2 Ru H C6H6]+[BF4]−
)
2
3
˚
F(3A)
F(4A)
F(1B)
F(2B)
F(3B)
F(4B)
4964(9)
4556(8)
7457(7) 2328(10) 153(8) sof=0.75
8551(7) 3193(6) 108(5) sof=0 75
2
3
U(eq)a (A ×10 )
˚
Atom
x
y
z
4549(21) 7796(25) 2126(19) 89(9) sof=0.25, Uiso
5565(30) 8793(30) 2642(25) 125(15) sof=0.25, Uiso
5187(22) 7492(26) 3270(21) 125(10) sof=0.25, Uiso
4154(25) 8480(27) 2706(22) 117(12) sof=0.25, Uiso
Ru
P(1)
P(2)
3541(1)
4665(1)
4316(1)
2033(1)
2510(1)
2482(1)
893(11)
2378(1) 34(1)
1716(1) 32(1)
3611(1) 35(1)
C(1A) 2819(12)
C(2A) 3316(10)
C(3A) 3115(12)
2886(7) 55(5) sof=0.78(4)
413(10) 2430(18) 85(9) sof=0.78(4)
765(13) 1623(13) 71(7) sof=0.78(4)
a Equivalent isotropic U(eq) is defined as one third of the trace of the
orthogonalized Uij tensor.
C(4A) 2458(19) 1507(18) 1370(16) 65(7) sof=0.78(4)
C(5A) 2007(8) 1885(10) 1846(10) 51(4) sof=0.78(4)
C(6A) 2178(10) 1592(13) 2632(10) 54(5) sof=0.78(4)
C(1B)
C(2B)
C(3B)
C(4B)
C(5B)
C(6B)
3170(36)
796(38) 1392(31) 39(12) sof=0.22(4),
Uiso
2505(60) 1281(53) 1368(57) 44(17) sof=0.22(4),
4. Preparation of the complexes
Uiso
2065(28) 1635(32) 2083(31) 33(10) sof=0.22(4),
The following general method was used for the
preparation of all the complexes: [{Ru(p6-arene)Cl2}2]
(0.5 mmol) in methanol (15 ml) was treated with
AgBF4/AgPF6 (2.0 mmol) and stirred at room tempera-
ture. After 30 min. the white ppt. of AgCl was filtered
off and the orange/yellow solution was treated with
EPh3 (1.5 mmol) dissolved in methanol (25 ml). Imme-
diately upon addition, color of the solution turned from
orange/yellow to yellow. It was stirred at room temper-
ature for 3 h, filtered to remove any solid and left for
slow crystallization in a refrigerator. Yellow crystal
separated out and color of the solution turned bluish.
The product was filtered, washed several times with
methanol, diethyl ether and dried in a vacuum (yield
40–60%).
Uiso
2445(37) 1220(39) 2775(28) 39(11) sof=0.22(4),
Uiso
3269(61)
584(54) 2870(39) 75(21) sof=0.22(4),
Uiso
494(37) 2114(31) 35(11) sof=0.22(4),
Uiso
3252(34)
C(7)
C(8)
C(9)
5803(4)
5844(5)
6668(6)
7491(6)
7485(5)
6647(5)
4310(4)
4707(5)
4387(7)
3704(7)
3309(6)
3613(5)
4912(5)
5451(6)
5634(6)
5273(6)
4727(6)
5185(4)
5702(5)
4536(5)
6341(6)
6493(6)
6003(7)
5342(6)
3466(5)
2676(5)
2017(6)
2125(6)
2892(6)
3562(5)
4952(5)
4538(6)
5043(7)
5951(7)
6362(6)
5875(5)
5015(8)
5939(6)
4743(8)
1968(6)
989(6)
534(7)
1015(8)
1975(8)
2463(6)
2185(5)
1455(5)
2007(3) 40(2)
2105(5) 52(3)
2292(5) 62(3)
2410(5) 65(3)
2342(5) 62(3)
2142(4) 44(2)
678(4) 40(2)
339(4) 47(2)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(25)
C(26)
C(24)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
B
1276(7) −446(5) 68(4)
1790(7) −881(5) 70(4)
2514(7) −552(5) 63(3)
It was also observed that in reactions involving
triphenylphosphine, just after addition of PPh3, a white
compound separated out. After filtration of this white
compound, we get hydrido complexes from the solution
and white compound analyses for tris (v-methoxy)
complex [(PPh3)3Ru(v-OMe)3Ru(PPh3)3]+.
2706(6)
3746(5)
3982(6)
4909(7)
5607(6)
5375(6)
1682(5)
1905(5)
4444(5)
1295(6)
449(6)
227(4) 49(3)
1582(4) 39(2)
1060(4) 52(3)
922(5) 64(3)
1307(5) 59(3)
1817(5) 59(3)
4156(4) 37(2)
4890(4) 49(3)
1957(4) 45(2)
5275(5) 57(3)
4963(5) 56(3)
4241(5) 66(3)
3850(5) 53(3)
4231(4) 40(2)
3956(5) 55(3)
4407(5) 61(3)
5118(5) 64(3)
5386(5) 62(3)
4946(4) 48(3)
3763(4) 37(2)
3911(5) 56(3)
3981(6) 70(4)
3933(6) 71(4)
3785(6) 70(4)
3690(5) 51(3)
2656(8) 70(4)
2884(6) 91(4) sof=0.75
2022(6) 124(5) sof=0.75
4.1. Selected data for the complexes
[RuH(p6-C6H6)(PPh3)2]BF4 (1a): color: yellow; m.p.
218°C; Anal. calcd. for BC42F4H37P2Ru: C, 63.70%; H,
4.67%; Found: C, 63.71%; H, 4.67%; IR (KBr, cm−1):
229(6)
826(6)
2617(5)
3158(6)
3282(7)
2856(7)
2313(6)
2191(5)
3588(5)
4419(6)
5248(6)
5259(7)
4437(7)
3609(6)
8276(9)
8502(7)
8972(8)
1
2004 w(Ru–H); NMR: H (l) 7.17–7.38 (br m, PPh3),
5.62 (sh s, C6H6), −9.0 (t, Ru–H); FABMS (NBA,
m/z): 705 ([M]+) 704 ([M–H]+), 625 ([M–H–C6H6]+),
363 ([M–H–C6H6–PPh3]+), 101 ([M–H–C6H6–PPh3–
PPh3]+).
[RuH(p6-C6H6)(AsPh3)2]PF6 (1b): color: yellow; m.p.
225°C; Anal. calcd. for As2C42F6H37PRu: C, 53.78%;
H, 3.92%; Found: C, 53.82%; H, 4.02%; IR (KBr,
cm−1): 2005 w(Ru–H); NMR: 1H (l) 7.2–7.8 (brm,
AsPh3), 5.65 (s,C6H6), −9.2 (s, Ru–H).
F(1A)
F(2A)

O. Singh Sisodia et al. / Journal of Organometallic Chemistry 560 (1998) 35–40
39
Table 3
53.70%, H, 4.64%; Found: C, 49.20%, H, 4.82%; IR
Selected bond distances (A) and angles (°) in [Ru(p6-
˚
1
(KBr, cm−1): 2012 w(Ru–H); NMR: H (l) 7.25–7.48
C6H6)(PPh3)2H]BF4
(brm, SbPh3), 2.15 (s, C6Me6), −9.62 (s, Ru–H).
Ru–H
Ru–P(1)
Ru–P(2)
1.62(9)
2.329(2)
2.327(2)
P(1)–Ru–P(2)
H–Ru–P(2)
H–Ru–P(1)
97.2(1)
85.1(31)
76.6(27)
[(PPh3)3Ru(v-OMe)3Ru(PPh3)3]PF6 (4): color: white;
m.p. 245°C; Anal. calcd. for C111H99F6O3P7Ru: C,
66.30%, H, 4.90%; Found C, 66.27%, H, 4.54%; NMR:
1H (l) 7.03–7.70 (brm, PPh3), 3.12 (s, OCH3).
[RuH(p6-C6H6)(SbPh3)2]PF6 (1c): color: yellow; m.p.
208°C; Anal. calcd. for C42F7H37PRuSb2: C, 48.90%,
H, 4.97%; Found: C, 48.62%, H, 3.62%; IR (KBr,
cm−1): 2008 w(Ru–H); NMR: 1H (l) 7.1–7.7 (brm,
SbPh3), 5.63 (s,C6H6), −9.36 (s, Ru–H).
s, singlet; brm, broad multiplet; d, doublet; t, triplet.
4.2. Crystallographic analysis
Diffraction data were collected with Siemens P4/PC
diffractometer from yellow prismatic crystal of dimen-
sions 0.52×0.28×0.26 mm in ꢀ, scan mode (2q
range from 3.0 to 55°). The crystal parameters along
with data collection details are recorded in Table 1.
Intensities were measured by the ꢀ scan method using
[RuH(p6-C10H14)(PPh3)2]PF6 (2a): color: pale yellow;
m.p. 190°C; Anal. calcd. for C46F6H45P3Ru: C, 60.90%,
H, 4.97%; Found: C, 61.24%, H, 6.81%; IR (KBr,
1
cm−1): 2020 w(RuH); NMR: H (l) 7.30–7.68 (brm,
PPh3), 5.39, 5.98 (AB pattern, C6H4), 2.88 (sp, CHMe2),
2.33 (s, CH3), 1.35 (d, CHMe2), −9.6 (t, Ru–H);
FABMS (NBA, m/z): 761 ([M]+), 760 ([M–H]+), 498
([M–H–PPh3]+), 363 ([M–H–PPh3–C10H14]+), 101
([M–H–C10H14–2PPh3]+).
˚
Mo–Kh radiation (u=0.71073 A). A variable scan
speed between 4.00–60.00° min−1 in ꢀ was used.
Throughout the data collection intensities of three
standard reflections were measured every 97 reflections
as a check of stability of the crystal and no decay was
observed. A total of 8424 reflections (2qB55°) were
measured and out of these 4118 reflections with F\
4.0| were used in solution and refinement of the struc-
tures.
[RuH(p6-C10H14)(AsPh3)2]PF6 (2b): color: yellow;
m.p. 178°C; Anal. calcd. for As2C46F6H45PRu: C,
55.50%, H, 4.53%; Found: C, 55.56%, H, 4.82%; IR
1
(KBr, cm−1): 2015 w(Ru–H); NMR: H (l) 7.30–7.68
(brm, AsPh3), 5.39, 5.98 (AB pattern, C6H4), 2.88 (sp,
CHMe2), 2.33 (s, CH3), 1.35 (d, CHMe2), −8.92 (s,
Ru–H).
The structure was solved by direct methods with
SIR-92 [8] and refined by block matrix least square
procedure using SHELXTL [9]. All the non hydrogen
atoms were refined with anisotropic thermal parame-
ters by full matrix least square method and hydrogen
atoms were calculated at the ideal positions and were
not refined. The function minimized was Sꢀ(F0−Fc)2
where ꢀ−1=|2(F)+0.0008F2 resulting in R=0.0589,
ꢀR=0.0663 and S=1.09. Crystallographic data are
recorded in Table 1. Fractional atomic coordinates,
U(eq) and selected bond lengths and angles are given
in Tables 2 and 3, respectively.
[RuH(p6-C10H14)(SbPh3)2]PF6 (2c): color: yellow;
m.p. 180°C; Anal. calcd. for C46F6H45PRuSb2: C,
50.08%. H, 4.14%; Found: C, 51.02%, H, 4.16%; IR
1
(KBr, cm−1): 2010 w(Ru–H); NMR: H (l) 7.2–7.8
(brm, SbPh3), 6.12, 6.30 (AB pattern, C6H4), 2.80 (m,
CHMe2), 2.26 (s, CH3), 1.32 (d, CHMe2).
[RuH(p6-C6Me6)(PPh3)2]PF6 (3a): color: yellow; m.p.
210°C; Anal. calcd. for C48F6H49P3Ru: C, 61.73%, H
5.25%; Found: C, 61.62%, H, 5.24%; IR (KBr, cm−1):
1
2020 w(Ru–H); NMR: H (l) 7.24–7.82 (brm, PPh3),
Acknowledgements
2.16 (s, C6Me6), −9.8 (t, Ru–H); FABMS (NBA,
m/z): 789 ([M]+), 788 ([M–H]+), 525 ([M–H–PPh3]+),
363 ([M–H–PPh3–C6Me6]+), 101 ([M–H–2PPh3–
C6Me6]+).
Thanks are due to CSIR, New Delhi for providing
financial assistance in the form of a project HRDG
01(1231) EMR-II/92. Thanks also due to the Head of
the Department of Chemistry for extending facilities
and the Head of RSIC, CDRI in Lucknow for extend-
ing analytical and spectral facilities. A special thanks is
due to Prof. M. Carmen Puerta, Prof. P. Valerga and
Manuel Jimenez Tenorio, Departamento de Qu´ımica
Inorga´nica, Universidad de Cadiz (Spain) for their en-
couragement, revision of the manuscript and for com-
pleting some calculations.
[RuH(p6-C6Me6)(AsPh3)2]PF6 (3b): color: yellow;
m.p. 208°C; Anal. calcd. for As2C48F6H49PRu: C,
53.70%, H, 5.09%; Found: C, 53.72%, H, 5.16%; IR
1
(KBr, cm−1): 2015 w(Ru–H); NMR: H (l) 7.31–7.82
(brm, AsPh3), 2.15 (s, C6Me6), −9.56 (s, Ru–H).
[RuH(p6-C6Me6)(SbPh3)2]PF6 (3c): color: yellow;
m.p. 210(d)°C; Anal. calcd. for C48F6H49PRuSb2: C,

40
O. Singh Sisodia et al. / Journal of Organometallic Chemistry 560 (1998) 35–40
[5] (a) D.S. Pandey, A. Mishra, R.L. Mishra, U.C. Agarwala,
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