Synthesis and reactivity of hydride and dihydrogen complexes of ruthenium with tris(pyrazolyl)borate and phosphite ligands

Article abstract of DOI:10.1016/j.jorganchem.2005.01.028

Chloro phosphite complexes RuClTpL(PPh₃) (1a, 1b) [L = P(OEt)₃, PPh(OEt)₂] and RuClTp[P(OEt)₃] ₂ (1c) [Tp = hydridotris(pyrazolyl)borate] were prepared by allowing RuClTp(PPh₃)₂

Full text of DOI:10.1016/j.jorganchem.2005.01.028

Journal of Organometallic Chemistry 690 (2005) 1726–1738
www.elsevier.com/locate/jorganchem
Synthesis and reactivity of hydride and dihydrogen complexes
of ruthenium with tris(pyrazolyl)borate and phosphite ligands
*
Gabriele Albertin , Stefano Antoniutti, Marco Bortoluzzi, Gianluigi Zanardo
`
Dipartimento di Chimica, Universita Caꢀ Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy
Received 10 December 2004; accepted 19 January 2005
Available online 25 February 2005
Abstract
Chloro phosphite complexes RuClTpL(PPh3) (1a, 1b) [L = P(OEt)3, PPh(OEt)2] and RuClTp[P(OEt)3]2 (1c) [Tp = hydrido-
tris(pyrazolyl)borate] were prepared by allowing RuClTp(PPh3)2 to react with an excess of phosphite. Treatment of the chloro com-
plexes 1 with NaBH4 in ethanol yielded the hydride RuHTpL(PPh3) (2a, 2b) and RuHTp[P(OEt)3]2 (2c) derivatives. Protonation
reaction of 2 with Brønsted acids was studied and led to thermally unstable (above 10 °C) dihydrogen [Ru(g2- H2)TpL(PPh3)]+
(3a, 3b) and [Ru(g2-H2)Tp{P(OEt)3}2]+ (3c) complexes. The presence of the g2-H2 ligand is indicated by short T1 min values and
JHD measurements of the partially deuterated derivatives. Aquo [RuTp(H2O)L(PPh3)]BPh4 (4), carbonyl [RuTp(CO)L(PPh3)]BPh4
(5), and nitrile [RuTp(CH3CN)L(PPh3)]BPh4 (6) derivatives [L = P(OEt)3] were prepared by substituting H2 in the g2-H2 derivatives
t
3. Vinylidene [RuTp{@C@C(H)R}L(PPh3)]BPh4 (7, 8) (R = Ph, Bu) and allenylidene [RuTp(@C@C@CR1R2)L(PPh3)]BPh4 (9–
11) complexes (R1 = R2 = Ph, R1 = Ph R2 = Me) were also prepared by allowing dihydrogen complexes 3 to react with the appro-
priate HC„CR and HC„CC(OH)R1R2 alkynes. Deprotonation of vinylidene complexes 7, 8 with NEt3 was studied and led to
acetylide Ru(C„CR)TpL(PPh3) (12, 13) derivatives. The trichlorostannyl Ru(SnCl3)TpL(PPh3) (14) compound was also prepared
by allowing the chloro complex RuClTpL(PPh3) to react with SnCl2 Æ2H2O in CH2Cl2.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Hydride; Dihydrogen; Tris(pyrazolyl)borate ligand; Phosphite ligands; Ruthenium; Vinylidene
1. Introduction
8 and 9 and for the ruthenium [4] are of the [RuTp-
(g2-H2)P2]+, [RuTp(g2-H2)PL]+ and RuTp*H(g2-H2)P
[P = PPh3, PiPr3 and P2 = 1,2-bis(diisopropylphos-
phine); L = CO, CH3CN; Tp* = hydridotris(3-isopro-
pyl-4-bromopyrazolyl)borate] type with the ligand
associated to the Tp ligand being tertiary phosphine,
carbonyl and acetonitrile. No dihydrogen complexes
with Tp and the phosphite P(OR)3 or PPh(OR)2, how-
ever, have been prepared although phosphites have
shown interesting properties in both the stabilization
and the reactivity of dihydrogen derivatives [6,7].
Since Kubasꢀ initial discovery [1] of the first dihydro-
gen complexes of transition metals, a large number of
g2-H2 derivatives have been prepared and their proper-
ties extensively studied [2,3]. The ancillary ligands used
in this chemistry involve mainly p-acceptors such as ter-
tiary phosphine, carbon monoxide and cyclopentadienyl
and only recently hydridotris(pyrazolyl)borate (Tp) has
been introduced as a supporting ligand in the chemistry
of classical and non-classical transition metal hydrides
[4,5]. The related complexes include metals of Groups
We are interested in the chemistry of classical and
non-classical transition metal hydrides and have re-
ported on the synthesis and reactivity of g2-H2 com-
*
Corresponding author. Tel.: +39 041 234 8555; fax: +39 041 234
plexes of manganese [7] and iron [6] triads of the
[M(g2-H2)(CO)nP5ꢀn
8917.
+
]
(M = Mn, Re; n = 1,2,3,4) and
E-mail address: albertin@unive.it (G. Albertin).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.01.028

G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
1727
[MX(g2-H2)P4]+ (M = Fe, Ru, Os; X = H, Cl, Br) types
2.2. Synthesis of complexes
stabilized by phosphite ligands. Recently, the use of
nitrogen donor ligands such as 1,2-bipyridine (bpy)
and 1,10-phenanthroline (phen) in the hydride chemistry
have allowed the synthesis of mixed-ligands [MH(N–
N)P3]+ and [M(g2-H2)(N–N)P3]2+ (M = Fe, Ru, Os;
N–N = bpy, phen; P = phosphite) complexes with phos-
phites and polypyridyls [8]. Now we have extended these
studies with the aim of introducing phosphite ligands
into the chemistry of tris(pyrazolyl)borate hydride com-
plexes and the results of these studies on the ruthenium,
which involve the synthesis and the reactivity of
new classical and non-classical hydride complexes, are
reported here.
The RuClTp(PPh3)2 was prepared following the
method previously reported [12].
2.2.1. RuClTpL(PPh3)(1) [L = P(OEt)3 (a),
PPh(OEt)2 (b)]
An excess of the appropriate phosphite (2.76 mmol)
was added to a solution of RuClTp(PPh3)2 (0.4 g,
0.46 mmol) in 15 mL of benzene and the reaction mix-
ture was refluxed for 3 h. The solvent was removed un-
der reduced pressure to give an oil which was triturated
with ethanol (3 mL). A yellow–brown solid separated
out by slow cooling of the solution, which was filtered
and dried under vacuum; yield: 1a 0.30 g (85%), 1b
0.32 g (86%). 1a: C33H40BClN6O3P2Ru (778.15): Calcd.
C, 50.95; H, 5.18; N, 10.80; Cl, 4.56. Found: C, 50.82; H,
5.24; N, 10.67; Cl, 4.71%. 1b: C37H40BClN6O2P2Ru
(810.04): Calcd. C, 54.86; H, 4.98; N, 10.37; Cl, 4.38.
Found: C, 54.97; H, 5.05; N, 10.26; Cl, 4.51%.
2. Experimental
2.1. General considerations
All synthetic work was carried out in an appropriate
atmosphere (Ar, N2) using standard Schlenk techniques
or a vacuum atmosphere dry-box. Once isolated, the
complexes were found to be relatively stable in air, but
were stored in an inert atmosphere at ꢀ25 °C. All
solvents were dried over appropriate drying agents,
degassed on a vacuum line, and distilled into vacuum-
tight storage flasks. RuCl3 Æ3H2O salt was a ChemPur
(USA) product, used as received. Potassium hydrido-
tris(pyrazolyl)borate (KTp) was prepared according to
a published procedure [9]. Phosphite PPh(OEt)2 was
prepared by the method of Rabinowitz and Pellon
[10], while P(OEt)3 was an Aldrich product purified by
distillation under nitrogen. Alkynes RC„CH (R = Ph,
tBu) and HC„CC(OH)R1R2 (R1 = R2 = Ph; R1 =
Ph, R2 = Me) were Aldrich products used without any
further purification. Lithium acetylide Li+[PhC„C]ꢀ
was prepared by reacting a slight excess of 1-alkyne
(PhC„CH, 2.42 mL, 22 mmol) with lithium (20 mmol,
0.14 g) in 10 mL of thf. Other reagents were purchased
from commercial sources in the highest available purity
and used as received. Infrared spectra were recorded on
a Nicolet Magna 750 FT-IR spectrophotometer. NMR
spectra (1H, 31P, 13C, 119Sn) were obtained on AC200
or AVANCE 300 Bruker spectrometers at temperatures
2.2.2. RuClTp[P(OEt)3]2 (1c)
An excess of P(OEt)3 (4.6 mmol, 0.76 mL) was added
to a solution of RuClTp(PPh3)2 (0.4 g, 0.46 mmol) in
15 mL of toluene and the reaction mixture was refluxed
for 4 h. The solvent was removed under reduced pres-
sure to give an oil which was triturated with ethanol
(2 mL). By slow cooling to ꢀ25 °C of the resulting solu-
tion, yellow microcrystals slowly separated out, which
were collected and dried under vacuum; yield: 0.25 g
(78%). C21H40BClN6O6P2Ru (681.86): Calcd. C, 36.99;
H, 5.91; N, 12.33; Cl, 5.20. Found: C, 37.14; H, 5.86;
N, 12.19; Cl, 5.08%.
2.2.3. RuHTpL(PPh3) (2) [L = P(OEt)3 (a),
PPh(OEt)2 (b)] and RuHTp[P(OEt)3]2 (2c)
To a solution of the appropriate chloro-complex
RuClTpL(PPh3) or RuClTp[P(OEt)3]2 (0.3 mmol) in
10 mL of ethanol was added an excess of NaBH4
(8 mmol, 0.30 g) in 10 mL of ethanol and the reaction
mixture refluxed for 1 h. The solvent was removed under
reduced pressure to give an oil from which the hydride
was extracted first with three 5-mL portions of CH2Cl2
and then with three 5-mL portions of benzene:petroleum
ether (40–60 °C) 1:1 mixture. The extracts were evapo-
rated to dryness and the obtained oil triturated with eth-
anol (2 mL). By slow cooling of the resulting solution, a
pale-yellow solid separated out, which was filtered and
crystallized from ethanol; yield: 2a 0.14 g (64%), 2b
0.15 g (66%), 2c 0.13 g (68%). 2a: C33H41BN6O3P2Ru
(743.55): Calcd. C, 53.31; H, 5.56; N, 11.30. Found: C,
53.20; H, 5.43; N, 11.18%. 2b: C37H41BN6O2P2Ru
(775.60): Calcd. C, 57.30; H, 5.33; N, 10.84. Found: C,
57.46; H, 5.24; N, 10.97%. 2c: C21H41BN6O6P2Ru
(647.42): Calcd. C, 38.96; H, 6.38; N, 12.98. Found: C,
38.77; H, 6.28; N, 12.85%.
1
between ꢀ90 and +30 °C, unless otherwise noted. H
and 13C spectra are referred to internal tetramethylsi-
lane; 31P{1H} chemical shifts are reported with respect
to 85% H3PO4, while 119Sn with respect to SnMe4, in
both cases with downfield shifts considered positive.
The COSY, HMQC and HMBC NMR experiments
were performed using their standard programs. The
SwaN-MR software package [11] was used to treat
NMR data. The conductivity of 10ꢀ3 mol dmꢀ3 solu-
tions of the complexes in CH3NO2 at 25 °C were mea-
sured with a Radiometer CDM 83.

1728
G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
2.2.4. [RuTp(g2-H2)L(PPh3)]þBF 4ꢀ (3)[L¼P(OEt)3 (a);
PPh(OEt)2(b)]and[RuTp g2-H2){P OEt)3}2]þBF 4ꢀ 3c
These complexes were prepared in solution in a NMR
tube at temperature below 10 °C. A typical experiment
involves the preparation of a solution of the appropriate
hydride (0.03 mmol) in CD2Cl2 (0.5 mL) in a NMR
tube, which was cooled to ꢀ80 °C. A slight excess of
HBF4 ÆEt2O (0.033 mmol, 4.7 lL) was added and the
tube transferred into the probe of the NMR instrument,
pre-cooled to ꢀ80 °C. The progress of the reaction was
which was filtered and crystallized from CH2Cl2 and
ethanol; yield 90 mg (62%). C59H63B2N7O3P2Ru
(1102.83): Calcd. C, 64.26; H, 5.76; N, 8.89. Found: C,
64.11; H, 5.81; N, 8.77%.
2.2.8. [RuTp{@C@C(H)R}{P(OEt)3}(PPh3)]BPh4
(7, 8) [R = Ph (7), t-Bu (8)]
An equimolar amount of HBF4 ÆEt2O (0.27 mmol,
39 lL) was added to a solution of RuHTp{P(OEt)3}-
(PPh3) (200 mg, 0.27 mmol) in 10 mL of CH2Cl2 cooled
to ꢀ196 °C. The reaction mixture was brought to
ꢀ10 °C, stirred for 10 min and then an excess of the
appropriate alkyne HC„CR (0.54 mmol) was added.
The resulting solution was left to reach the room tem-
perature and stirred for about 2 h. The solvent was re-
moved under reduced pressure to give a brown oil
which was treated with ethanol (3 mL) containing an ex-
cess of NaBPh4 (0.54 mmol, 0.185 g). A pink solid sepa-
rated out from the resulting solution which was filtered
and crystallized from CH2Cl2 and ethanol; yield: 7
188 mg (60%), 8 195 mg (63%). 7: C65H66B2N6O3P2Ru
(1163.91): Calcd. C, 67.08; H, 5.72; N, 7.22. Found: C,
66.95; H, 5.78; N, 7.15%. 8: C63H70B2N6O3P2Ru
(1143.92): Calcd. C, 66.15; H, 6.17; N, 7.35. Found: C,
66.28; H, 6.10; N, 7.23%.
1
monitored by H and 31P{1H} spectra in the tempera-
ture range from ꢀ80 to 20 °C.
2.2.5. [RuTp(H2O){P(OEt)3}(PPh3)]BF4 (4)
This complex was obtained in an attempt to isolate
the dihydrogen complex [RuTp(g2-H2){P(OEt)3}(PPh3)]
BF4. To a solution of RuHTp[P(OEt)3](PPh3) (100 mg,
0.13 mmol) in 10 mL of diethylether cooled to
ꢀ196 °C was added a slight excess of HBF4 ÆEt2O
(20 lL, 0.14 mmol). The reaction mixture was brought
to ꢀ10 °C and stirred for about 30 min. A gummy prod-
uct separated out from the solution which, by addition
of ethanol (2–3 mL) slowly gave a yellow solid which
was filtered and crystallized from ethanol and diethyle-
ther; yield 60 mg (55%). C33H42B2F4N6O4P2Ru
(847.36): Calcd. C, 46.78; H, 5.00; N, 9.92. Found: C,
46.63; H, 4.91; N, 10.04%.
2.2.9. [RuTp{@C@C@C(Ph)R}{P(OEt)3}(PPh3)]-
BPh4 (9, 10) [R = Ph (9), Me (10)] and
2.2.6. [RuTp(CO){P(OEt)3}(PPh3)]BPh4 (5)
An equimolar amount of HBF4 ÆEt2O (0.13 mmol,
[RuTp{@C@C@C(Ph)2}{P(OEt)3}2]BPh4 (11)
An equimolar amount of HBF4 ÆEt2O (0.13 mmol,
19 lL) was added to a solution of RuHTp{P(OEt)3}-
(PPh3) (100 mg, 0.13 mmol) in 5 mL of CH2Cl2 cooled
to ꢀ196 °C. The reaction mixture was brought to
ꢀ20 °C, stirred for 10 min and then an excess of the
appropriate propargylic alcohol HC„CC(OH)(Ph)R
(0.26 mmol) in 5 mL of CH2Cl2 was added. The result-
ing solution was left to reach the room temperature, stir-
red for 4 h and then the solvent removed under reduced
pressure. The oil obtained was triturated with ethanol
(3 mL) containing an excess of NaBPh4 (0.26 mmol,
89 mg). A purple solid slowly separated out from the
resulting solution which was filtered and crystallized
from CH2Cl2 and ethanol; yield: 9 94 mg (58%), 10
94 mg (61%), 11 97 mg (64%). 9: C72H70B2N6O3P2Ru
(1252.02): Calcd. C, 69.07; H, 5.64; N, 6.71. Found: C,
68.91; H, 5.60; N, 6.63%. 10: C67H68B2N6O3P2Ru
(1189.95): Calcd. C, 67.63; H, 5.76; N, 7.06. Found: C,
67.82; H, 5.69; N, 6.94%. 11: C60H70B2N6O6P2Ru
(1155.89): Calcd. C, 62.35; H, 6.10; N, 7.27. Found: C,
62.20; H, 6.34; N, 7.17%.
19 lL) was added to
a
solution of RuHTp-
{P(OEt)3}(PPh3) (100 mg, 0.13 mmol) in 10 mL of
CH2Cl2 cooled to ꢀ196 °C. The reaction mixture was al-
lowed to stand under a CO atmosphere (1 atm) and
slowly left to reach the room temperature. After 3 h of
stirring, the solvent was removed under reduced pres-
sure to give an oil which was treated with ethanol
(2 mL) containing an excess of NaBPh4 (0.26 mmol,
89 mg). A yellow solid slowly separated out from the
resulting solution which was filtered and crystallized
from CH2Cl2 and ethanol; yield 102 mg (72%).
C58H60B2N6O4P2Ru (1089.79): Calcd. C, 63.92; H,
5.55; N, 7.71. Found: C, 64.06; H, 5.49; N, 7.66%.
2.2.7. [RuTp(CH3CN){P(OEt)3}(PPh3)]BPh4 (6)
An equimolar amount of HBF4 ÆEt2O (0.13 mmol,
19 lL) was added to
a
solution of RuHTp-
{P(OEt)3}(PPh3) (100 mg, 0.13 mmol) in 5 mL of CH2Cl2
cooled to ꢀ196 °C. The reaction mixture was brought to
ꢀ10 °C, stirred for 10 min and then an excess of CH3CN
(1 mmol, 52 lL) added. The resulting solution was left
to reach the room temperature and stirred for 3 h. The
solvent was removed under reduced pressure to give
an oil which was triturated with ethanol containing an
excess of NaBPh4 (0.26 mmol, 89 mg). A pale yellow so-
lid slowly separated out from the resulting solution,
2.2.10. Ru(C„CR)Tp{P(OEt)3}(PPh3) (12, 13)
[R = Ph (12), t-Bu (13)]
An excess of triethylamine (0.3 mmol, 42 lL) was
added to a solution of the appropriate vinylidene
[RuTp{@C@C(H)R}{P(OEt)3}(PPh3)]BPh4 (7, 8) (0.10

G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
1729
exc. NaBH4
EtOH
L = P(OEt)3 a, PPh(OEt)2 b
mmol) in 5 mL of CH2Cl2 and the reaction mixture was
RuClTpL(PPh3)
RuHTpL(PPh3)
stirred for 3 h. A white solid ([NHEt3]BPh4) separated
out from the solution which was filtered and rejected.
The solution was evaporated to dryness under reduced
pressure to give an oil which was triturated with ethanol
(2 mL). By cooling of the resulting solution to ꢀ25 °C a
yellow solid separated out, which was filtered and dried
under vacuum; yield: 12 72 mg (85%), 13 67 mg (82%).
12: C41H45BN6O3P2Ru (843.67): Calcd. C, 58.37; H;
5.38; N, 9.96. Found: C, 58.19; H, 5.33; N, 10.04%.
13: C39H49BN6O3P2Ru (823.68): Calcd. C, 56.87; H,
6.00; N, 10.20. Found: C, 57.00; H, 5.88; N, 10.32%.
2
exc. NaBH4
EtOH
RuClTp{P(OEt)3}2
RuHTp{P(OEt)3}2
2c
Scheme 2.
Good analytical data were obtained of all the com-
pounds 1–2, which are white or pale yellow solids stable
in air and in solution of all the common organic sol-
vents, where they behave as non electrolytes [13]. The
IR and NMR spectra (Table 1) support the proposed
formulation.
The infrared of both chloro and hydrido complexes
show the characteristic mBH band of the Tp ligand at
2484–2461 cmꢀ1, while a medium-intensity absorption
at 1994–1948 cmꢀ1 attributed to mRuH was observed in
2.2.11. Ru(SnCl3)Tp{P(OEt)3}(PPh3) (14)
An excess of SnCl2 Æ2H2O (0.26 mmol, 59 mg) was
added to a solution of [RuClTp{P(OEt)3}(PPh3)] BPh4
(1a) (100 mg, 0.13 mmol) in 20 mL of CH2Cl2 and the
resulting suspension was stirred for 10 h. The volume
of the solvent was reduced to about 5 mL by evapora-
tion under reduced pressure and the solid formed was
filtered, washed with ethanol and dried under vacuum.
The complex was extracted from the solid obtained with
five 5-mL portions of CH2Cl2 and the extracts were con-
centrated to about 3–4 mL. A yellow solid separated out
whose precipitation was completed by addition of etha-
nol. The solid was filtered and dried under vacuum;
yield: 69 mg (55%). C33H40BCl3N6O3P2RuSn (967.59):
Calcd. C, 40.96; H, 4.17; N, 8.69; Cl, 10.99. Found: C,
40.79; H, 4.11; N, 8.82; Cl, 11.07%.
1
the spectra of the hydride derivatives 2. The H NMR
spectra confirm the presence of the hydridotris(pyraz-
olyl)borate ligand showing, between 8.12 and 5.53 ppm,
the characteristic multiplets of the pyrazole hydrogen
atoms of the Tp group. The signals due to the phosph-
ites P(OEt)3 and PPh(OEt)2 are also present in the spec-
tra of compounds 1, 2. Furthermore, the 1H NMR
spectra of the mixed-ligand RuHTpL(PPh3) (1a, 1b)
hydride complexes show a multiplet near ꢀ14 ppm
attributed to the hydride resonances coupled to the
phosphorus nuclei of the phosphine. Taking into ac-
count that the 31P{1H} NMR spectra appear as an AB
multiplet, the spectra can be simulated as the X part
of an ABX spectrum with the parameters reported in
Table 1. Values for the two JPH of 24 and of 32 or
34 Hz, respectively, were calculated.
The proton spectrum of the phosphite RuHTp-
{P(OEt)3}2 (2c) complex, instead, appears as a triplet
at ꢀ13.91 ppm with JPH of 33 Hz. The related 31P spec-
trum is a sharp singlet at 160.5 ppm. These data support
the formulation proposed for the new Tp complexes 1,
2, whose geometry should be of the types I and II, re-
ported in Chart 1.
Hydride RuHTpL(PPh3) (2a, 2b) and RuHTp-
{P(OEt)3]2 (2c) complexes react with the Brønsted acids
HBF4 ÆEt2O or CF3SO3H to give the dihydrogen
[Ru(g2-H2)TpL(PPh3)]+ (3a, 3b) and [Ru(g2-H2)Tp-
{P(OEt)3}2]+ (3c) derivatives (Scheme 3), which are sta-
ble below 5–10 °C. At higher temperatures the loss of H2
takes place, thus preventing the separation of the dihy-
drogen complexes in the solid state. Spectroscopic data
(Table 2), however, strongly support the formation of
the dihydrogen derivatives 3.
3. Results and discussion
When using benzene as a solvent, the chloro complex
[12] RuClTp(PPh3)2 reacts with phosphites to give the
mixed-ligands RuClTpL(PPh3) (1a, 1b) derivatives,
while using toluene the reaction gives the RuClTp-
{P(OEt)3}2 (1c) complex in a good yield, as shown in
Scheme 1.
The related RuClTp{PPh(OEt)2}2 (1d) compound,
however, was obtained under all conditions, as a mix-
ture of products which were not separated.
Treatment of the chloro complexes 1a, 1b, 1c with
NaBH4 in refluxing ethanol gave the corresponding hy-
dride RuHTpL(PPh3) (2a, 2b) and RuHTp[P(OEt)3]2
(2c), which were isolated in good yields and character-
ized (Scheme 2).
exc. L
RuClTp(PPh3)2
RuClTpL(PPh3)
benzene, ∆
L = P(OEt)3 a, PPh(OEt)2 b
1
exc. P(OEt)3
RuClTp(PPh3)2
RuClTp{P(OEt)3}2
The protonation reaction was carried out at variable
1
toluene, ∆
1c
temperatures and was monitored by H and 31P NMR
Scheme 1.
spectra. The addition of HBF4 ÆEt2O or CF3SO3H to 2

Table 1
Selected IR and NMR spectroscopic data for ruthenium complexes
Compound
IRa m (cmꢀ1
)
Assgnt
1H NMRb d (J, Hz)
Assgnt
Spin system
AB
31P{1H} NMRb,c d (J, Hz)
1a
1b
RuCl(Tp){P(OEt)3}(PPh3)
2480 m
2478 m
mBH
8.02–7.60 m
3.51 m
0.98 t
Ph + Tp
CH2
CH3
dA 140.9
dB 45.6
JAB = 55
RuCl(Tp){PPh(OEt)2}(PPh3)
mBH
7.85–5.66 m
3.83 m
3.43 m
1.11 t
Ph + Tp
CH2
AB
dA 167.2
dB 42.5
JAB = 45
CH3
0.88 t
1c
2a
RuCl(Tp){P(OEt)3}2
2484 m
mBH
8.01–6.04 m
3.70 m
1.16 s
Tp
A2
141.8 s
CH2
CH3
RuH(Tp){P(OEt)3}(PPh3)
2473 m
1994 m
mBH
mRuH
7.84–5.53 m
3.65 m
3.35 m
Ph + Tp
CH2
AB
dA 161.6
dB 73.0
JAB = 63
0.87 t
CH3
H
ABX spin syst
dX ꢀ14.14
JAX = 24
JBX = 34
2b
RuH(Tp){PPh(OEt)2}(PPh3)
2482 m
mBH
7.89–5.54 m
3.95 m
3.34 m
Ph + Tp
CH2
AB
dA 181.7
dB 71.6
JAB = 53
1.01 t
0.76 t
CH3
H
ABX spin syst
dX ꢀ14.04
JAX = 24
JBX = 32
2c
RuH(Tp){P(OEt)3}2
2461 m
1948 m
mBH
mRuH
8.12–6.12 m
3.71 m
1.18 t
Tp
A2
160.5 s
CH2
CH3
H
ꢀ13.91 t
JPH = 33
3a
3b
½Ruðg2-H2ÞðTpÞfPðOEtÞ3gðPPh3ÞꢁþBFꢀ4
½Ruðg2-H2ÞðTpÞfPPhðOEtÞ2gðPPh3ÞꢁþBFꢀ4
7.98–5.81 md
3.49 m
3.19 m
Ph + Tp
CH2
AB
AB
dA 128.6
dB 42.1
JAB = 51
1.05 t
ꢀ8.97 br
CH3
H2
8.00–5.84 me
3.60 m
3.30 m
Ph + Tp
CH2
dA 157.2
dB 43.4
JAB = 43.5
1.14 t
0.93 t
CH3
H2
ꢀ8.90 br
Line missing

3c
4
½Ruðg2-H2ÞðTpÞfPðOEtÞ3g2ꢁþBFꢀ4
7.98–6.25 me
3.60 m
1.18 t
Tp
A2
131.7 s
CH2
CH3
H2
ꢀ9.21 br
[RuTp(H2O){P(OEt)3}(PPh3)]BF4
2484 w
mBH
7.88–6.00 m
3.66 m
3.29 m
Ph + Tp
CH2
AB
dA 133.1
dB 47.8
JAB = 45
2.13 s,br
1.08 t
H2O
CH3
5
6
[RuTp(CO){P(OEt)3}(PPh3)]BPh4
2494 w
1998 s
mBH
mCO
7.83–5.92 m
3.58 m
3.35 m
Ph + Tp
CH2
AB
AB
dA 121.7
dB 38.6
JAB = 49
1.05 t
CH3
[RuTp(CH3CN){P(OEt)3}(PPh3)]BPh4
2484 w
2287 w
mBH
mCN
7.90–6.00 m
3.56 m
3.25 m
1.69 s
Ph + Tp
CH2
dA 131.8
dB 44.8
JAB = 53
CH3CN
CH3 phos
1.00 t
7
8
[RuTp{@C@C(H)Ph}{P(OEt)3}(PPh3)]BPh4
[RuTp{@C@C(H)t-Bu}{P(OEt)3}(PPh3)]BPh4
2486 w
1653 m
1636 m
mBH
mC@C
7.98–5.63 m
5.68 q
Ph + Tp
@CH
AB
AB
dA 116.6
dB 37.1
JAB = 49
JPH = JPH = 4
3.43 m
1.04 t
CH2
CH3
2482 w
1672 m
1653 m
mBH
mC@C
8.12–5.93 m
4.59 t
Ph + Tp
@CH
dA 120.4
dB 39.9
JAB = 49
JPH = 3
3.60 m
3.39 m
1.07 t
CH2
CH3 phos
t-Bu
1.03 s
9
[RuTp{@C@C@CPh2}{P(OEt)3}(PPh3)]BPh4
[RuTp{@C@C@C(Me)Ph}{P(OEt)3}(PPh3)]BPh4
2486 w
1948 s
mBH
mC@C@C
8.02–5.91 m
3.75 m
3.55 m
Ph + Tp
CH2
AB
AB
dA 123.9
dB 42.5
JAB = 55
1.08 t
CH3
10
2484 w
1956 s
mBH
mC@C@C
8.03–5.89 m
3.66 m
3.50 m
2.28 s
Ph + Tp
CH2
dA 122.9
dB 41.1
JAB = 53
@CCH3
CH3 phos
1.06 t
11
[RuTp{@C@C@CPh2}{P(OEt)3}2]BPh4
2482 w
1952 s
mBH
mC@C@C
8.40–5.83 m
3.65 m
1.20 t
Ph + Tp
CH2
CH3
A2
127.0 s
(continued on next page)

1732
G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
H
H
B
N
B
N
N
N
N
N
N
N
N
N
N
N
Ru
Cl
Ru
H
L
L
L'
1 ( I )
L'
2 ( II )
Chart 1. L = P(OEt)3 or PPh(OEt)2, L0 = PPh3; L = L0 = P(OEt)3.
+
H
H
B
B
N
N
N
N
N
N
N
N
N
N
N
N
H
HBF4•Et2O
Ru
H
Ru
or CF3SO3H
H
L
L
L'
L'
2
3
Scheme 3. L0 = PPh3, L = P(OEt)3 (a), PPh(OEt)2 (b); L = L0 =
P(OEt)3 (c).
caused the disappearance of the hydride multiplet near
ꢀ14 ppm and the appearance of a broad signal near
ꢀ9.0 ppm attributed to the g2-H2 ligand. Measurements
of T1 on these signals gave T1 min values of 8.0–7.1 ms
(Table 2) in agreement with the presence of a dihydro-
gen derivative [14].
Further support for the presence of the g2-H2 ligand
came from the measurement of the JHD values of the iso-
topomer [Ru(g2-HD)TpLL0]+ derivatives. These HD
complexes were prepared by addition of deuterated tri-
flic acid, CF3SO3D, to the hydrides 2 in CD2Cl2. In
1
the hydride region, the H NMR spectra show a rela-
tively sharp triplet of multiplets of 1:1.4:1 intensity.
The increased intensity of the center peak of the triplet
of the HD resonances is due to the presence of a small
amount of H2 species resulting from the incomplete deu-
teration of the triflic acid, while the splitting of each sig-
nal of the triplet is attributable to the coupling with the
phosphorus of the phosphines, with 2JPH(HD) of 9 Hz for
3c and with values of about 7–8 Hz for 3a and 3b. From
this triplet values of 31.5 and 32.0 Hz for JHD were mea-
sured, which confirm the formation of dihydrogen deriv-
atives. From the JHD values the H–H distances were
calculated [15], which are reported in Table 2. Values be-
2
˚
tween 0.90 and 0.91 A were observed for our g -H2 com-
plexes 3, which are strictly comparable with those
reported for related tris(pyrazolyl)borate ruthenium
dihydrogen complexes containing tertiary phosphine
of the [Ru(g2-H2)Tp(PPh3)2]BF4, [Ru(g2-H2)Tp(dppe)]-
BF4, [Ru(g2-H2)TpL(PPh3)]BF4 (L = CO, CH3CN) type

G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
1733
Table 2
T1 min (200 MHz) and JHD NMR data for some dihydrogen and hydride complexes and calculated H–H distances
˚
rH–H (A)
Compound
T (K)
d (ppm)
T1 min (ms)
JHD (Hz)
3a [Ru(g2-H2)(Tp){P(OEt)3}(PPh3)]+
3b [Ru(g2-H2)(Tp){PPh(OEt)2}(PPh3)]+
3c [Ru(g2-H2)(Tp){P(OEt)3}2]+
2a RuH(Tp){P(OEt)3}(PPh3)
a
208
211
204
203
ꢀ8.95
ꢀ9.1
7.1
8.0
7.2
225
32.0
31.5
31.5
1.05a
1.07
1.06
0.83b
0.85
0.84
0.90c
0.91
0.91
ꢀ9.2
ꢀ14.04
The H–H distances were calculated [16] from T1 min values for static regimes of the H2 ligand.
b
c
The H–H distances were calculated [16] from T1 min values for fast rotation of the H2 ligand.
H–H distances were calculated from the JHD values for the HD complexes using the equation [15]: rH–H = 1.44–0.0168 (JHD).
[4d,4e]. In tris(pyrazolyl)borate Ru (II) dihydrogen com-
plexes, therefore, the nature of the supporting ligands
does not seem to have a strong influence on the H–H
distance of the g2-H2 group.
The H–H bond length in the H2 ligand can also be
calculated from T1 min values [16]. The results for com-
plexes 3 are reported in Table 2 for both a fast and a
slow rotation model and are not comparable with those
calculated from the JHD values. The H–H distance of
CH2Cl2. Carbonyl 5 and acetonitrile 6 complexes were
also obtained by substituting the g2-H2 ligand in 3a
and were isolated as yellow solids.
Interesting is the reaction of the dihydrogen com-
plexes with terminal alkyne RC„CH (Scheme 5), which
gives the vinylidene [17] [RuTp{@C@C(H)R}LL0]+ (7,
8) cations, isolated as pale-pink BPh4 salts. The substitu-
tion of the g2-H2 ligand by the alkyne probably give a
[Ru](g2-RC„CH) intermediate complex, which tau-
tomerises [18] to yield the final vinylidene derivatives
7, 8.
˚
0.90–0.91 A calculated from JHD, in fact, are just inter-
˚
mediate between the two possible values of 1.05–1.07 A
˚
(slow rotation) and 0.83–0.85 A (fast rotation), calcu-
Propargyl alcohol HC„CC(OH)R1R2 also reacts
with dihydrogen complex 3a giving a deep-purple
lated from the T1 min values. Similar results were found
in other dihydrogen ruthenium (II) derivatives [8b].
In the temperature range between +20 and ꢀ80 °C
the 31P{1H} NMR spectra of the dihydrogen complexes
appear as an AB quartet for [RuTp(g2-H2)L(PPh3)]+
(3a, 3b) while a sharp singlet is observed for [RuTp-
(g2-H2){P(OEt)3}2]+ (3c) derivative, in agreement with
the geometry proposed in Scheme 3.
H2O
[RuTp(H2O)LL']+
4
CO
[Ru(η2-H2)TpLL']+
[RuTp(CO)LL']+
3
5
The preparation of complexes 2, 3 highlights that
also phosphite ligands can be used to stabilize classical
and non-classical tris(pyrazolyl)borate Ru hydride com-
plexes. A comparison with the related carbonyl or phos-
phine [Ru(g2-H2)TpLP]+ derivatives [4] shows,
however, that the introduction of phosphite ligands into
Tp complexes decreases the thermal stability of the g2-
H2 derivatives like 3. This is somewhat unexpected in
light of our previous results on the ability of phosphite
to stabilize g2-H2 complexes. Probably, in Tp-hydride
chemistry the influence of the supporting ligands on
the properties and the stabilization of g2-H2 ligand is
rather restricted.
CH3CN
[RuTp(CH3CN)LL']+
6
Scheme 4. L = P(OEt)3, L0 = PPh3.
+
H
B
N
N
N
N
N
N
H
R
HC≡CR
Ru
C
C
L
L'
7, 8
3.1. Reactivity of g2-H2 complexes
+
H
[Ru(η2-H2)TpLL']+
B
N
3
The g2-H2 ligand is labile in the [RuTp(g2-H2)LL0]+
(3) cations and can be easily substituted by several li-
gands allowing new RuTp complexes to be prepared.
Some examples have been reported in Schemes 4 and 5.
At first, the aquo complex 4 was obtained in an at-
tempt to isolate the g2-H2 complex in the solid state,
due to the presence of traces of H2O in the solvent. It
was also obtained as a pale-yellow solid by adding an
excess of H2O to a solution of g2-H2 complex 3a in
N
N
N
N
N
R2
R1
HC≡CC(OH)R1R2
Ru
C
C
C
L
L'
9, 10, 11
Scheme 5. L = P(OEt)3, L0 = PPh3, R = Ph (7), tBu (8), R1 = R2 = Ph
(9), R1 = Ph, R2 = Me (10); L = L0 = P(OEt)3, R1 = R2 = Ph (11).

1734
G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
Table 3
13C{1H} NMR data for selected ruthenium complexes
Compounda
13C{1H} NMR d (J, Hz)
Assgnt
6
7
8
[RuTp(CH3CN){P(OEt)3}(PPh3)]BPh4
165–106 m
ABX spin syst
dX 142.9
JAX = 4.2
JBX = 1.4
62.0 d
Ph + Tp
CH3CN
CH2
CH3 phos
CH3CN
16.1 d
3.67 s
[RuTp{@C@C(H)Ph}{P(OEt)3}(PPh3)]BPh4
ABX spin syst
dX 376.4
JAX = 17.8
JBX = 21.7
165–106 m
114.1 s
Ca
Ph + Tp
Cb
CH2
64.2 d
15.9 d
CH3
[RuTp{@C@C(H)t-Bu}{P(OEt)3}(PPh3)]BPh4
ABX spin syst
dX 373.3
JAX = 22.0
JBX = 17.5
165–106 m
121.2s
Ca
Ph + Tp
Cb
CH2
63.8d
33.2s
C(CH3)3
C(CH3)3
CH3 phos
32.2s
15.9d
9
[RuTp{@C@C@CPh2}{P(OEt)3}(PPh3)]BPh4
ABX spin syst
dX 319.0
JAX = 25.6
JBX = 17.8
204.4 s
Ca
Cb
163.0 s
Cc
163–106 m
63.0 d
15.9 d
Ph + Tp
CH2
CH3
10
[RuTp{@C@C@C(Me)Ph}{P(OEt)3}(PPh3)]BPh4
ABX spin syst
dX 321.6
JAX = 17.5
JBX = 25.7
200.5 s
Ca
Cb
164.4 s
Cc
164–106 m
63.1 d
31.6 s
Ph + Tp
CH2
@CCH3
CH3 phos
16.0 d
11
[RuTp{@C@C@CPh2}{P(OEt)3}2]BPh4
319.2 t
JPC = 7
201.9 s
163.8 s
165–122 m
62.3 d
Ca
Cb
Cc
Ph + Tp
CH2
CH3
16.1 d
12
Ru(C„CPh)Tp{P(OEt)3}(PPh3)
144–104 m
110.4 m
60.5 d
Ph + Tp
Ca
CH2
16.1 d
CH3

G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
1735
Table 3 (continued)
Compounda
Ru(C„Ct-Bu)Tp{P(OEt)3}(PPh3)
13C{1H} NMR d (J, Hz)
Assgnt
13
145–104 m
116.0 s
Ph + Tp
Cb
ABX spin syst
dX 99.6
Ca
JAX = 23
JBX = 21.5
60.2 d
CH2
33.4 s
29.9 s
16.1 d
C(CH3)3
C(CH3)3
CH3 phos
a
In CD2Cl2 at 25 °C.
solution from which the allenylidene [RuTp(@C@C@
CR1R2)LL0]+ (9–11) cations were isolated as BPh4 salts
and characterized. The reaction probably gives hydroxo-
vinylidene [RuTp{@C@C(H)CR1R2OH}LL0]+ interme-
diate by tautomerization of the alkyne on the metal
center. The loss of water from this intermediate allows
the formation of the final allenylidene species 9–11.
Despite the large number of reported vinylidene [17–
19] and allenylidene [20,21] complexes of ruthenium, rel-
atively few contain tris(pyrazolyl)borate as supporting
ligand [22]. The use of the dihydrogen complexes 3 as
precursors allows the facile synthesis of the new
mixed-ligand derivatives 9–11 with phosphite and
tris(pyrazolyl)borate.
The multiplicity of the signal at 142.9 ppm is due to
the coupling of the carbon with the phosphorus nuclei
and can be easily simulated using an ABX model, with
the parameters reported in Table 3. Values of 4.2 and
1.4 Hz were observed for JCP, in agreement with the
N-coordination of the nitrile.
3
The IR spectra of the vinylidene [RuTp{@C@
C(H)R}LL0]BPh4 (7, 8) complexes show two medium-
intensity bands at 1672–1636 cmꢀ1, which are charac-
teristic [17,18] of the vinylidene ligands. The presence
1
of this ligand, however, is confirmed by both the H
and 13C NMR spectra, which show the characteristic
signals of the @C@C(H)R group. A quartet at
5.68 ppm for 7 and a triplet at 4.59 ppm for 8, attrib-
uted to the vinylidene @C(H)R proton, are observed
The new complexes are yellow (4–6), pink (7, 8), and
deep-purple (9–11) solids stable in air and in a solution
of polar organic solvents, where they behave as 1:1 elec-
trolytes [13]. Analytical and spectroscopic data (Tables 1
and 3) support the proposed formulation. The IR spec-
tra show the medium-intensity mBH band at 2494–
2482 cmꢀ1 of the Tp ligand, whose presence in all the
1
in the H NMR spectra of the complexes. In the spec-
tra of [RuTp{@C@ C(H)C(CH3)3}LL0]BPh4 (8) a sin-
glet at 1.03 ppm is also present due to the methyl
t
resonance of the Bu substituent. Furthermore, a mul-
tiplet at 376.4 ppm for 7 and at 373.3 ppm for 8 are
present in the 13C NMR spectra, which are attributed
to the Ca resonances of the vinylidene ligands. In the
spectra a singlet at 114.1 ppm for 7 and at 121.2 ppm
for 8 are also present, attributed to the Cb carbon res-
onance of the Ru@C@C(H)R vinylidene ligand. The
HMQC and the HMBC experiments confirms these
attributions showing the correlation between the 13C
signal at 114–121 ppm with the multiplet of the CH
resonances at 5.68–4.59 ppm in the proton spectra. In
the temperature range between +20 and ꢀ80 °C the
31P{1H} NMR spectra appear as a AB multiplet, in
agreement with the presence of two different phosphine
ligands. On the basis of the spectroscopic data, a
geometry of the type of Scheme 5 can be reasonably
proposed for the vinylidene derivatives.
1
complexes 4–11 is confirmed by the H NMR spectra,
which show the characteristic signals of the pyrazole
protons between 8.40 and 5.63 ppm.
The 1H NMR spectrum of the aquo-complex 4 shows
a slightly broad signal at 2.13 ppm, attributed [23] to the
protons of the coordinated H2O. The 31P{1H} NMR
spectrum appears as an AB multiplet, in agreement with
the proposed formulation.
The infrared spectrum of the [RuTp(CO)LL0]BPh4
(5) complex shows a strong band at 1998 cmꢀ1, attrib-
1
uted to the mCO of the carbonyl ligand, while the H
NMR spectrum shows, as expected, the signals of the
Tp and the phosphine ligands. An AB multiplet, finally,
is observed in the 31P{1H} NMR spectrum.
The presence of the nitrile ligand in [RuTp(CH3CN)-
LL0]BPh4 (6) is confirmed by the IR spectrum, which
shows a weak band at 2287 cmꢀ1 due to the mCN of
the CH3CN group. Further support comes from the
13C spectra, which show a singlet at 3.67 ppm and a mul-
tiplet at 142.9 ppm, attributed to the methyl and the CN
carbon resonances, respectively, of the CH3CN ligand.
The IR spectra of the allenylidene [RuTp(@C@C@
CR1R2)LL0]BPh4 (9–11) complexes show a strong band
at 1956–1948 cmꢀ1 attributed to mC@C@C of the propadi-
enylidene [20,21] ligand. Strong support for the presence
of the @C@C@CR1R2 group comes from the 13C NMR
spectra (Table 3), which show the characteristic reso-
nance at 321–319 ppm for Ca, at 204–200 ppm for Cb,

1736
G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
and at 164–163 ppm for Cc of the coordinate allenylid-
ene ligand. Furthermore, the Ca carbon resonances ap-
pear as a triplet (11) or as a multiplet (9, 10) due to the
coupling with the phosphorus nuclei. The multiplet can
also be simulated using an ABX model with the param-
eters reported in Table 3. Finally, the 31P spectra are AB
multiplets for 9 and 10, while a singlet is observed for 11,
so confirming the geometry proposed in Scheme 5 for
the allenylidene derivatives.
Vinylidene [RuTp{@C@C(H)R}LL0]BPh4 (7, 8)
complexes can be easily deprotonated with base (NEt3)
to give the related acetylide RuTp(C„CR)LL0 (12, 13)
derivatives, which were isolated in the solid state and
characterized (Scheme 6).
Acetylide complexes can also be formed by reacting
the chloro-complex 1a with an excess of Li+C„CRꢀ in
thf (Scheme 7), but in this case the yield is low due to
the formation of byproducts. The chloro-complex also
reacts with SnCl2 in CH2Cl2 to give the trichlorostan-
nyl [Ru(SnCl3)TpLL0] (14) complex, which was isolated
as a yellow solid and characterized (Scheme 7).
Compound 14 is generated by insertion of SnCl2 into
the Ru–Cl bond of the precursor 1a. Such a process is
well known and has been thoroughly studied due to
the ability of the trichlorostannyl ligand to promote or
modify the catalytic activity of transition metal com-
plexes [24,25].
Good analytical data were obtained for complexes
12–14, which are yellow solids stable in air and in a solu-
tion of common organic solvents, where they behave as
non-electrolytes [13]. Infrared and NMR data (Tables 1
and 3) support the proposed formulation. In particular,
the presence of the acetylide ligand in 12, 13 is indicated
by the medium-intensity mC„C band at 2081 cmꢀ1 (12)
and at 2091 cmꢀ1 (13) observed in the IR spectra. Fur-
ther support comes from the 13C spectra, which show
the signals of the Ca carbon atom of the acetylide as a
multiplet at 110.4 ppm for 12 and at 99.6 ppm for 13.
In the latter complex, the singlet at 116.0 ppm is attrib-
uted to the Cb carbon resonance, while the signals at
33.4 and 29.9 ppm are due to the carbons of the tBu sub-
stituent. The 31P{1H} NMR spectra appear as a AB
multiplet, in agreement with the geometry proposed in
Scheme 5.
The presence of the SnCl3 ligand in the [Ru(SnCl3)-
TpLL0] (14) complex is confirmed by the 119Sn NMR
spectra, which show a multiplet at ꢀ218 ppm (from
SnMe4) due to the coupling with the phosphorus nuclei
of the phosphines. Taking into account that the 31P
spectrum is a AB multiplet with the satellites due to
the coupling of the phosphorus atoms with the NMR-
active 117Sn and 119Sn nuclei, the multiplet of the 119Sn
spectrum can be simulated using a ABM (M = 119Sn)
model with the parameters reported in Table 1. On the
basis of these data, a geometry of the type of Scheme
7 can reasonably be proposed for the trichlorostannyl
derivative.
+
H
H
B
B
N
N
N
N
N
N
N
N
N
N
N
N
H
R
NEt3
Ru
C
C
Ru
C
CR
L
L
L'
L'
7, 8
12, 13
t
Scheme 6. L = P(OEt)3, L0 = PPh3; R = Ph (12), Bu (13).
H
4. Conclusions
B
N
N
N
N
An easy route for the introduction of phosphite li-
gands in the chemistry of classical and non-classical
tris(pyrazolyl)borate ruthenium (II) hydride complexes
has been achieved using RuClTp(PPh3)2 as a precursor.
Mixed-ligand RuHTpLL0 hydrides and [Ru(g2-H2)-
TpLL0]+ dihydrogen derivatives were prepared and
information on the H–H distances of g2-H2 complexes
were obtained from T1 measurements and JHD values.
New tris(pyrazolyl)borate complexes containing vinyli-
dene and allenylidene ligands of the [RuTp{@C@
C(H)R}LL0]BPh4 and [RuTp(@C@C@CR1R2)LL0]-
BPh4 type, as well as acetylide Ru(C„CR)TpLL0
and trichlorostannyl Ru(SnCl3)TpLL0 derivatives, were
also obtained using the dihydrogen complexes as a
precursor.
N
N
Li+[C≡CR]-
Ru
C
CR + decomp. products
thf
L
L'
12
H
RuClTpLL'
B
1a
N
N
N
N
N
N
SnCl2
Ru
SnCl3
CH2Cl2
L
L'
14
Scheme 7. L = P(OEt)3, L0 = PPh3; R = Ph.

G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
1737
(c) P.J. Desrosiers, L. Cai, Z. Lin, R. Richards, J. Halpern, J.
Am. Chem. Soc. 113 (1991) 4173–4184.
Acknowledgments
[15] (a) D.M. Heinekey, T.A. Luther, Inorg. Chem. 35 (1996) 4396–
4399;
The financial support of MIUR (Rome) – PRIN 2004
– is gratefully acknowledged. We thank Daniela Baldan
for technical assistance.
(b) P.A. Maltby, M. Schlaf, M. Steinbeck, A.J. Lough, R.H.
Morris, W.T. Klooster, T.F. Koetzle, R.C. Srivastava, J. Am.
Chem. Soc. 118 (1996) 5396–5407;
(c) W.A. King, X.-L. Luo, B.L. Scott, G.J. Kubas, K.W. Zilm, J.
Am. Chem. Soc. 118 (1996) 6782–6783.
References
[16] K.A. Earl, G. Jia, P.A. Maltby, R.H. Morris, J. Am. Chem. Soc.
113 (1991) 3027–3039.
[17] (a) M.I. Bruce, Chem. Rev. 91 (1991) 197–257;
(b) M.C. Puerta, P. Valerga, Coord. Chem. Rev. 193 (1999) 977–
1025;
[1] G.J. Kubas, R.R. Ryan, B.I. Swanson, P.J. Vergamini, H.J.
Wasserman, J. Am. Chem. Soc. 106 (1984) 451–452.
[2] (a) G.J. Kubas, Metal dihydrogen and r-bond complexes, Kluwer
Academic Publishers, New York, 2001;
(c) C. Bruneau, P.H. Dixneuf, Acc. Chem. Res. 32 (1999) 311–323;
(d) B.M. Trost, F.D. Toste, A.B. Pinkerton, Chem. Rev. 101 (2001)
2067–2096;
(b) M. Peruzzini, R. Poli, Recent Advances in Hydride Chemistry,
Elsevier, Amsterdam, 2001.
(e) J. Louie, R.H. Grubbs, Angew. Chem., Int. Ed. 40 (2001) 247–
249.
[3] (a) P. Jessop, R.H. Morris, Coord. Chem. Rev. 121 (1992) 155–284;
(b) D.M. Heinekey, W.J. Oldham Jr., Chem. Rev. 93 (1993) 913–
926;
[18] (a) For some recent papers see: C.-Y. Wong, C.-M. Che, M.C.W.
Chan, K.-H. Leung, D.L. Phillips, N. Zhu, J. Am. Chem. Soc.
126 (2004) 2501–2514;
(c) R.H. Crabtree, Angew. Chem., Int. Ed. 32 (1993) 789–805;
(d) M.A. Esteruelas, L.A. Oro, Chem. Rev. 98 (1998) 577–588;
(e) S. Sabo-Etienne, B. Chaudret, Coord. Chem. Rev. 178–180
(1998) 381–407;
´
(b) H. Aneetha, M. Jimenez-Tenorio, M.C. Puerta, P. Valerga,
K. Mereiter, Organometallics 22 (2003) 2001–2013;
(c) P. Alvarez, E. Lastra, J. Gimeno, M. Bassetti, L.R. Falvello,
J. Am. Chem. Soc. 125 (2003) 2386–2387;
(f) G. Jia, C.-P. Lau, Coord. Chem. Rev. 190–192 (1999) 83–108.
[4] (a) B. Moreno, S. Sabo-Etienne, B. Chaudret, A. Rodriguez, F.
Jalon, S. Trofimenko, J. Am. Chem. Soc. 117 (1995) 7441–7451;
(b) Y.Z. Chen, W.C. Chan, C.P. Lau, H.S. Chu, H.L. Lee, G.
Jia, Organometallics 16 (1997) 1241–1246;
(d) M. Baya, P. Crochet, M.A. Esteruelas, E. Gutierrez-Puebla,
A.M. Lopez, J. Modrego, E. On˜ate, N. Vela, Organometallics
19 (2000) 2585–2596;
(e) D.J. Bernad, M.A. Esteruelas, A.M. Lopez, J. Modrego,
M.C. Puerta, P. Valerga, Organometallics 18 (1999) 4995–5003;
(f) H. Werner, J. Chem. Soc., Chem. Commun. (1997) 903–910.
[19] (a) J.R. Lomprey, J.P. Selegue, J. Am. Chem. Soc. 114 (1992)
55185523;
´ ´
(c) M. Jimenez-Tenorio, M.A. Jimenez-Tenorio, M.C. Puerta, P.
Valerga, Inorg. Chim. Acta 259 (1997) 77–84;
(d) C. Bohanna, M.A. Esteruelas, A.V. Gomez, A.M. Lopez,
M.P. Martinez, Organometallics 16 (1997) 4464–4468;
(e) S.M. Ng, Y.Q. Fang, C.P. Lau, W.T. Wong, G. Jia,
Organometallics 17 (1998) 2052–2059.
(b) R.M. Bullock, J. Chem. Soc., Chem. Commun. (1989) 165–167;
´
(c) E. Bustelo, M. Jimenez-Tenorio, M.C. Puerta, P. Valerga,
Organometallics 18 (1999) 4563–4573;
[5] (a) U.E. Bucher, T. Lengweiler, D. Nanz, W. von Philipsborn,
L.M. Venanzi, Angew. Chem., Int. Ed. Engl. 29 (1990) 548–549;
(b) W.J. Oldham Jr., A.S. Hinkle, D.M. Heinekey, J. Am. Chem.
Soc. 119 (1997) 11028–11036.
´
´
(d) E. Bustelo, J. Carbo, A. Lledos, K. Mereiter, M.C. Puerta, P.
Valerga, J. Am. Chem. Soc. 125 (2003) 3311–3321;
(e) C. Ciardi, G. Reginato, L. Gonsalvi, I. de los Rios, A.
Romerosa, M. Peruzzini, Organometallics 23 (2004) 2020–2026.
[20] (a) D. Touchard, P.H. Dixneuf, Coord. Chem. Rev. 178 (1998)
409–429;
[6] (a) G. Albertin, S. Antoniutti, E. Bordignon, J. Am. Chem. Soc.
111 (1989) 2072–2077;
(b) P. Amendola, S. Antoniutti, G. Albertin, E. Bordignon,
Inorg. Chem. 29 (1990) 318–324;
(b) M.I. Bruce, Chem. Rev. 98 (1998) 2797–2858;
(c) V. Cadierno, M.P. Gamasa, J. Gimeno, Eur. J. Inorg. Chem.
(2001) 571–591.
(c) G. Albertin, S. Antoniutti, D. Baldan, E. Bordignon, Inorg.
Chem. 34 (1995) 6205–6210.
[7] (a) G. Albertin, S. Antoniutti, M. Bettiol, E. Bordignon, F.
Busatto, Organometallics 16 (1997) 4959–4969;
´
(b) G. Albertin, S. Antoniutti, S. Garcia-Fontan, R. Carballo, F.
[21] (a) S. Rigaut, K. Kostuas, D. Touchard, J.-Y. Saillard, S. Golhen,
P.H. Dixneuf, J. Am. Chem. Soc. 126 (2004) 4072–4073;
(b) T.B. Wen, Z.Y. Zhou, G. Jia, Organometallics 22 (2003)
4947–4951;
Padoan, J. Chem. Soc., Dalton Trans. (1998) 2071–2081.
[8] (a) G. Albertin, S. Antoniutti, M. Bortoluzzi, Inorg. Chem. 43
(2004) 1328–1335;
(c) K. Ilg, H. Werner, Chem. Eur. J. 8 (2002) 2812–2820;
´
(d) M.I. Buil, M.A. Esteruelas, A.M. Lopez, E. On˜ate, Organo-
metallics 22 (2003) 162–171;
(b) G. Albertin, S. Antoniutti, A. Bacchi, C. DꢀEste, G. Pelizzi,
Inorg. Chem. 43 (2004) 1336–1349;
´
(e) E. Bustelo, M. Jimenez-Tenorio, K. Mereiter, M.C. Puerta, P.
(c) G. Albertin, S. Antoniutti, S. Pizzol, J. Organomet. Chem. 689
(2004) 1639–1647.
Valerga, Organometallics 21 (2002) 1903–1911;
(f) V. Cadierno, S. Conejero, M.P. Gamasa, J. Gimeno, M.A.
´
Rodrıguez, Organometallics 21 (2002) 203–209;
[9] (a) S. Trofimenko, Inorg. Synth. 12 (1970) 99–109;
(b) S. Trofimenko, J. Am. Chem. Soc. 88 (1966) 1122–1123.
[10] R. Rabinowitz, J. Pellon, J. Org. Chem. 26 (1961) 4623–4626.
[11] G. Balacco, J. Chem. Inf. Comput. Sci. 34 (1994) 1235–1241.
[12] (a) N.W. Alcock, I.D. Burns, K.S. Claire, A.F. Hill, Inorg. Chem.
31 (1992) 2906–2908;
´
(g) P. Gonzales-Herrero, B. Weberndo¨rfer, K. Ilg, J. Wolf, H.
Werner, Organometallics 20 (2001) 3672–3685;
(h) M.I. Bruce, P.J. Low, K. Costuas, J.-F. Halet, S.P. Best,
G.A. Heath, J. Am. Chem. Soc. 122 (2000) 1949–1962.
[22] (a) C. Slugovc, R. Schmid, K. Kirchner, Coord. Chem. Rev. 185–
186 (1999) 109–126;
(b) F. Hill, J.D.E.T. Wilton-Ely, Inorg. Synth. 33 (2002) 206–208.
[13] W.J. Geary, Coord. Chem. Rev. 7 (1971) 81–122.
[14] (a) D.G. Hamilton, R.H. Crabtree, J. Am. Chem. Soc. 110 (1988)
4126–4136;
´ ´
(b) M.A. Jimenez-Tenorio, M. Jimenez-Tenorio, M.C. Puerta, P.
Valerga, Organometallics 16 (1997) 5528–5535;
(c) B. Buriez, I.D. Burns, A.F. Hill, A.J.P. White, D.J. Williams,
J.D.E.T. Wilton-Ely, Organometallics 18 (1999) 1504–1516;
(b) M.T. Bautista, K.A. Earl, P.A. Maltby, R.H. Morris, C.T.
Schweitzer, A. Sella, J. Am. Chem. Soc. 110 (1988) 7031–7036;

1738
G. Albertin et al. / Journal of Organometallic Chemistry 690 (2005) 1726–1738
(d) Y. Arikawa, Y. Nishimura, H. Kawano, M. Onishi, Organo-
metallics 22 (2003) 3354–3356;
[24] (a) G. Consiglio, F. Morandini, G. Ciani, A. Sironi, M.
Kretschmer, J. Am. Chem. Soc. 105 (1983) 1391–1392;
(b) B. Moreno, S. Sabo-Etienne, F. Dahan, B. Chaudret, J.
Organomet. Chem. 498 (1995) 139–145.
(e) C. Gemel, P. Wiede, K. Mereiter, V.N. Sapunov, R. Schmid,
K. Kirchner, J. Chem. Soc., Dalton Trans. (1996) 4071–4076;
(f) G. Trimmel, C. Slugovc, P. Wiede, K. Mereiter, V.N. Sapunov,
R. Schmid, K. Kirchner, Inorg. Chem. 26 (1997) 1076–1083.
´
[25] (a) D. Fernandez, M.I. Garcia-Seijo, T. Kegl, G. Petocz, L.
Kollar, M.E. Garcia-Fernandez, Inorg. Chem. 41 (2002) 4435–
4443;
(b) T. Yamakawa, T. Fujita, S. Shinoda, Chem. Lett. (1992) 905.
[23] G. Albertin, S. Antoniutti, A. Bacchi, M. Boato, G. Pelizzi, J.
Chem. Soc., Dalton Trans. (2002) 3313–3320.