Preparation and Reactivity of Mixed-Ligands Hydride Complexes [RuHCl(CO)(PPh3)2{P(OR)3}]

Article abstract of DOI:10.1002/zaac.201900037

Mixed-ligands hydride complexes [RuHCl(CO)(PPh₃)₂{P(OR)₃}] (2) (R = Me, Et) were prepared by allowing [RuHCl(CO)(PPh₃)₃] (1) to react with an excess of phosphites P(OR)₃ in refluxing benzene. Treatment of hydrides 2 first with triflic acid and next with an excess of hydrazine afforded hydrazine complexes [RuCl(CO)(κ¹-NH₂NHR1)(PPh₃)₂{P(OR)₃}]BPh₄ (3, 4) (R1 = H, CH₃). Diethylcyanamide derivatives [RuCl(CO)(N≡CNEt₂)(PPh₃)₂{P(OR)₃}]BPh₄ (5) were also prepared by reacting 2 first with HOTf and then with N≡CNEt₂. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [RuHCl(CO)(PPh₃)₂{P(OEt)₃}] (2b).

Full text of DOI:10.1002/zaac.201900037

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201900037
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Preparation and Reactivity of Mixed-Ligands Hydride Complexes
[RuHCl(CO)(PPh3)2{P(OR)3}]
Gabriele Albertin,*[a] Stefano Antoniutti,[a] and Jesús Castro*[b]
Abstract.
Mixed-ligands
hydride
complexes
(3, 4) (R1
=
H, CH3). Diethylcyanamide derivatives
[RuHCl(CO)(PPh3)2{P(OR)3}] (2) (R = Me, Et) were prepared by al-
lowing [RuHCl(CO)(PPh3)3] (1) to react with an excess of phosphites
[RuCl(CO)(NϵCNEt2)(PPh3)2{P(OR)3}]BPh4 (5) were also prepared
by reacting 2 first with HOTf and then with NϵCNEt2. The complexes
P(OR)3 in refluxing benzene. Treatment of hydrides
2 first were characterized spectroscopically and by X-ray crystal structure de-
with triflic acid and next with an excess of hydrazine afforded hydraz-
ine complexes [RuCl(CO)(κ1-NH2NHR1)(PPh3)2{P(OR)3}]BPh4
termination of [RuHCl(CO)(PPh3)2{P(OEt)3}] (2b).
The hydride [RuHCl(CO)(PPh3)3] (1) reacts with an excess
of phosphite P(OR)3 in benzene to give mixed-ligands deriva-
tives [RuHCl(CO)(PPh3)2{P(OR)3}] (2), which were isolated
and characterized (Scheme 1).
Introduction
Previous reports from our laboratories dealt with studies on
the synthesis and reactivity of hydride-carbonyl complexes of
osmium [OsHCl(CO)(PPh3)L] [L = P(OMe)3 and P(OEt)3],
which allowed the preparation of new organic azide and
hydrazine derivatives [OsCl(κ1-N3R)(CO)(PPh3)2L]BPh4 and
[OsCl(CO)(κ1-NH2NHR)(PPh3)2L]BPh4.[1] The interesting
properties shown by these mixed-ligands carbonyl complexes
prompted us to extend study to ruthenium[2] with the aim of
testing whether related hydride-carbonyl complexes may be
prepared and how they properties change. The results of these
studies, which involve the preparation of mixed-ligands hy-
drazine and diethylcyanamide complexes of ruthenium and the
crystallographic structure determination of [RuHCl(CO)–
(PPh3)2{P(OEt)3}], are reported herein.
Scheme 1. R = Me (a), Et (b).
The reaction proceeds with the substitution of only one PPh3
ligand affording the new hydride-carbonyl derivatives contain-
ing two PPh3 and one phosphite as supporting ligands. Good
analytical data were obtained for complexes 1 and 2, which
were isolated as yellow solids stable in air and in solution of
common organic solvents, where they behave as either non-
electrolytes.[4] Their IR and NMR spectroscopic data support
the proposed formulation, which was further confirmed by
X-ray crystal structure determination of the complex
[RuHCl(CO)(PPh3)2{P(OEt)3}] (2b). Figure 1 shows the
ORTEP[5] plot and selected bond lengths and angles are given
in Table 1.
Results and Discussion
The hydride-carbonyl complex [RuHCl(CO)(PPh3)3] (1) had
been prepared by reacting RuCl3·3H2O with PPh3 in refluxing
2-methoxyethanol and aqueous formaldehyde.[3] We found that
1 can be prepared in good yield by refluxing the dichloro com-
pound [RuCl2(PPh3)3] in ethanol in the presence of Zn dust.
The addition of the metal is crucial for successful synthesis,
otherwise only traces of hydride complex are obtained. No
other characterizable species was obtained from this reaction,
which represents an easy and efficient method for the prepara-
tion of this precursor.
* Prof. Dr. G. Albertin
E-Mail: albertin@unive.it
* Prof. Dr. J. Castro
E-Mail: jesusc@uvigo.es
[a] Dipartimento di Scienze Molecolari e Nanosistemi – DSMN
Università Ca’ Foscari Venezia, Campus Scientifico
Via Torino 155
30172 Venezia Mestre, Italy
[b] Departamento de Química Inorgánica
Facultade de Química
Figure 1.
[RuHCl(CO)(PPh3)2{P(OEt)3}] (2b).
ORTEP[5]
view
of
the
complex
The compound contains three phosphane ligands, organized
in a meridional configuration, and one carbonyl and one chlo-
rine ligands, trans to each other. One hydride ligand completes
Universidade de Vigo
Edificio de Ciencias Experimentais
36310 Vigo, Galicia, Spain
Z. Anorg. Allg. Chem. 2019, 645, 688–693
688
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Table 1. Selected bond lengths /Å and angles /° for 2b.
Ru(1)–H(1)
Ru(1)–P(1)
Ru(1)–P(3)
C(1)–O(1)
1.60(4)
Ru(1)–C(1)
Ru(1)–P(2)
Ru(1)–Cl(1)
1.825(7)
2.3775(15)
2.4630(15)
2.3604(17)
2.3602(15)
1.137(7)
C(1)–Ru(1)–P(1)
C(1)–Ru(1)–P(3)
P(1)–Ru(1)–P(2)
P(1)–Ru(1)–P(3)
88.7(2)
C(1)–Ru(1)–P(2)
C(1)–Ru(1)–Cl(1) 176.2(2)
P(2)–Ru(1)–P(3) 159.75(5)
P(1)–Ru(1)–Cl(1) 95.17(6)
P(3)–Ru(1)–Cl(1) 89.15(5)
92.42(18)
90.00(18)
101.06(6)
99.10(6)
P(2)–Ru(1)–Cl(1) 87.09(5)
H(1)–Ru(1)–C(1)
H(1)–Ru(1)–P(2)
H(1)–Ru(1)–Cl(1) 91.1(15)
85.1(15)
81.2(14)
H(1)–Ru(1)–P(1)
H(1)–Ru(1)–P(3)
Ru(1)–C(1)–O(1)
173.4(15)
79.0(14)
178.8(6)
Figure 2.
[RuHCl(CO)(PPh3)2{P(OEt)3}] (2b).
Schematic
view
of
the
complex
the octahedral environment for the RuII metal atom. Among
phosphanes, there is one phosphite ligand, situated trans to
the hydride ligand, and two triphenylphosphines trans to each
other.[6]
The Ru–P bond lengths range between 2.3602(15) and
2.3775(15) Å, and there is no difference between the phos-
phine and phosphite coordination distances.
The IR spectra of the mixed-ligands hydride complexes
[RuHCl(CO)(PPh3)2{P(OR)3}] (2) show one strong band at
1957 (2a) and 1956 cm–1 (2b) attributed to the ν(CO) of the
carbonyl ligand. These bands fall at a value slightly higher
than that of the related complex 1, in agreement with the better
π-acceptor properties of phosphite P(OR)3 with respect to
PPh3. In the spectra a weak band at 1886 (2a) and 1903 cm–1
(2b) is also present and was attributed to the ν(RuH) of the
This could sound surprising, since differences due to σ- and
π-bonding of phosphane and phosphine ligands are well-
known and, for example, Ru–P distances are clearly different
when they are trans to similar ligand, as Cp or related
ones.[2d,7] But in the case of the title compound 2b, probably
the higher π-acidity of the phosphite is balanced out by the
hydride in trans position.[8] In any case, the Ru–P distances
formed by the phosphines (2.37 Å in average) are comparable
to those found for complexes with similar arrangements, as the
trans Ru–P distances of 2.358 and 2.396 Å found for
RuH(CO)Cl(PPh3)3.[9]
The carbonyl Ru–C bond length, 1.825(7) Å, is only slightly
shorter than that found in the tris(triphenylphosphine) com-
pound RuH(CO)Cl(PPh3)3 [1.837(6) Å],[9] whereas the C–O
distance, 1.137(7) Å, does not show difference with reported
values for that compound, 1.141(6) Å. The Ru–Cl bond length
2.4630(15) Å (trans to the carbonyl ligand) is also slightly
shorter than that in the aforementioned compound
[2.499(1) Å].
1
hydride. The presence of such a ligand is confirmed by the H
NMR spectra, which show a doublet of triplets at –5.62 (2a)
and –5.74 ppm (2b) due to the hydride ligand coupled with the
31P nuclei of phosphine. The value of one JHP is in the range
177–174 Hz, whereas the other falls at 21.0–20.5 Hz suggest-
ing that the hydride is trans to one phosphine and cis to the
other two. In addition, in the temperature range between +20
and –80 °C, the 31P{1H} NMR spectra appear as AX2 mul-
tiplets suggesting that the two PPh3 are magnetically equiva-
lent and different from the phosphite. On this basis, mer ar-
rangement II (Scheme 1) may be proposed in solution for
mixed-ligands hydrides 2, like that found in the solid state
(Figure 1).
Hydrazine and Cyanamide Complexes
Hydride complexes 1 and 2 reacted with triflic acid at low
1
temperature (–80 °C) with evolution of H2 – detected by H
The two trans PPh3 ligands are bent towards the position NMR – and probable formation of a triflate species like
occupied by the hydride ligand, with a trans P–Ru–P angle [RuCl(κ1-OTf)(CO)(PPh3)2{P(OR)3}] [A]. Unfortunately, these
of 159.75(5)° and obtuse cis P–Ru–P angles of 99.10(6) and species are unstable also in solution and cannot be isolated.
101.06(6)°. This bending is usual in hydride compounds, prob- However, they can be used as precursors to prepare new com-
ably due to the scarce steric hindrance of the hydrogen plexes. In fact, treatment of the triflate complexes formed by
atom,[9,10] together with the high steric requirements of the protonation of 2 with an excess of hydrazine afforded the cat-
PPh3 ligands. The trans Cl–Ru–carbonyl angle, 176.2(2)°, is ionic complexes [RuCl(CO)(κ1-NH2NHR1)(PPh3)2{P(OR)3}]+
however close to theoretical 180°. Cis angles in the (3, 4) [R1 = H (3), CH3 (4); R = Me (a), Et (b)] which were
Cl–Ru–carbonyl meridional plane are acute for OC–Ru–P(1), isolated as tetraphenylborate salts and characterized (Scheme 2).
88.7(2)°, and obtuse for Cl–Ru–P(1) angle, 95.17(6)°, un-
Diethylcyanamide NϵCNEt2 also reacted with the triflate
doubtedly due to the relative disposition of P(OEt)3 as can be species [A] to give the cyanamide derivatives
seen in Figure 2(left), where is apparent the steric limitation [RuCl(CO)(NϵCNEt2)(PPh3)2{P(OR)3}]BPh4 (5) in good
on the chlorine position due to the ethoxy group of the phos- yields (Scheme 3).
phite ligand (whose phosphorus atom is hidden by the metal
Instead, treatment of the triflate complex [A] with organic
atom). Obviously the inaccuracy of the position of the hydride azide R2N3 did not afford any stable compound but only de-
in X-ray diffraction technique prevents any comment about its composition products (Scheme 4).
geometrical parameters. The Ru(1)–C(1)–O(1) angle,
178.8(6)°, is not surprising.
This result is rather unexpected because the related osmium
triflate compounds [OsCl(κ1-OTf)(CO)(PPh3)2{P(OR)3}]
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groups of the NH2NH2 ligand, respectively. The presence of
two resonances for the NH2 protons also suggests end-on coor-
dination of the hydrazine. The proton NMR spectra of methyl-
hydrazine complexes 4a and 4b also show a broad signal at
2.55–2.50 ppm attributed to the metal-bonded NH2 group and
a multiplet at 3.11–3.06 ppm of the NH protons of methylhy-
drazine. A doublet at 1.62 ppm (4a) and 1.59 ppm (4b) also
appears in the spectra of methylhydrazine derivatives due to
the methyl substituent of the CH3NHNH2 ligand. In the tem-
perature range between +20 and –80 °C the 31P{1H} NMR
spectra of 3 and 4 appear as AX2 multiplets suggesting the
magnetic equivalence of the two phosphines PPh3 different
from the phosphite P(OR)3.
Scheme 2. R1 = H (3), CH3 (4); R = Me (a), Et (b).
These spectroscopic data support the proposed formulation
for the hydrazine complexes 3 and 4 but do not allow to unam-
biguously assign them one among arrangements I, II, or III in
solution (Scheme 5).
Scheme 3. R = Me (a), Et (b).
Scheme 5. Possible geometries.
Scheme 4. R2 = ArCH2 or Ph.
However, the IR spectra of complexes 3 and 4 show the
quickly reacted with organic azides to give azide derivatives ν(CO) as a strong band at 1971–1982 cm–1, a value, which is
[OsCl(CO)(κ1-N3R2)(PPh3)2{P(OR)3}]BPh4, which are stable only slightly higher than those of the precursors
and isolable.[1] The ruthenium fragment, instead, is not able [RuHCl(CO)(PPh3)2{P(OR)3}] (2) (due to complex charge),
to stabilize azide as a ligand. However, both hydrazine and suggesting that a good σ-donor ligand such as Cl– should be
diethylcyanamide can be stabilized by the carbonyl fragments in trans position with respect to the CO, as observed in 2. On
[RuCl(CO)(PPh3)2{P(OR)3}]+ allowing the preparation of new these bases, arrangement II may be tentatively proposed in
derivatives.[11] Hydrazine complexes of ruthenium have been solution for the hydrazine derivatives.
previously reported with several ligands including arene, phos-
The IR spectra of the cyanamide complexes
phine, isocyanide, cyclopentadienyl, and tris(pyrazolyl)borate [RuCl(CO)(NϵCNEt2)(PPh3)2{P(OR)3}]BPh4 (5) show a me-
and have been studied as models of the dinitrogen dium-intensity band at 2273 cm–1 (5a) and 2278 cm–1 (5b) at-
fixation process.[2d,e,h,12,13] The use of the hydride tributed to the ν(NC) of the diethylcyanamide. In the spectra
[RuHCl(CO)(PPh3)2{P(OR)3}] as a precursor allowed the syn- a strong band at 1975–1977 cm–1 also appears due to the
1
thesis of mixed-ligands hydrazine derivatives.
ν(CO) of the carbonyl ligand. The H NMR spectra confirm
The new complexes 3–5 were all isolated as yellow or the presence of the cyanamide ligand showing the characteris-
orange solids stable in air and in solution of polar organic sol- tic signals of the substituents at 2.52 ppm q (5a) and 2.55 ppm
vents, where they behave as 1:1 electrolytes.[4] Analytical and q (5b) of the methylene and at 0.70 ppm t (5a) and 0.73 ppm
spectroscopic data (IR and NMR) supported the proposed for- t (5b) of the methyl protons of the CH3CH2 group of the
mulation.
NϵCNEt2 ligand. In the spectra the signals of the PPh3 and
The IR spectra of the hydrazine complexes [RuCl(CO)(κ1- P(OR)3 and of the BPh4 anion also appear. The 31P NMR spec-
NH2NHR1)(PPh3)2{P(OR)3}]BPh4 (3, 4) show two or three tra are AX2 multiplets suggesting that the two PPh3 are magnet-
bands of medium or weak intensity in the 3353–3267 cm–1 ically equivalent and different from the phosphite. On the basis
region attributed to the ν(NH) of the hydrazine ligand, the of these data and taking into account that the ν(CO) values are
presence of which is confirmed by the 1H NMR spectra, comparable with those of hydrazine derivatives 3 and 4, we
which, for complex 3b, show two broad resonances at δ = 3.40 tentatively propose a geometry in solution of type IV for dieth-
and 2.95 ppm attributed to the coordinated and free NH2 ylcyanamide derivatives 5 (Scheme 6).
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[RuCl2(PPh3)3] (0.25 g, 0.26 mmol), zinc dust (60 mg, 0.9 mmol), and
15 mL of ethanol. The reaction mixture was refluxed for 3 h, cooled to
room temperature, and an excess of the appropriate phosphite P(OR)3
(0.52 mmol) was added. The reaction mixture was refluxed for 45 min,
filtered, and the volume was reduced to about 3 mL by evaporation of
the solvent under reduced pressure. By slow cooling to –25 °C of the
resulting solution yellow microcrystals separated out, which were fil-
tered and crystallized from ethanol (yield Ն 35%). Method 2: An
excess of the appropriate phosphite P(OR)3 (0.45 mmol) was added to
a solution of [RuHCl(CO)(PPh3)3] (0.16 mmol, 250 mg) in 10 mL of
benzene and the reaction mixture was refluxed for 45 min. The solvent
was removed under reduced pressure to give an oil, which was tritu-
rated with ethanol (2 mL). By slow cooling to –25 °C of the resulting
solution a yellow solid slowly separated out, which was filtered and
crystallized from ethanol (yield Ն 80%). 2a: IR (KBr): ν˜ = (νCO)
1957 (s); (νRuH) 1886 (w) cm–1. 1H NMR (CD2Cl2, 20 °C): δ = 7.79–
7-30 (m, 30 H, Ph), 3.27 (dd, 9 H, CH3), –5.62 (dt, JHP = 177.0, JHP
= 21.0, 1 H, hydride) ppm. 31P{1H} NMR (CD2Cl2, 20 °C): δ = AX2
spin syst, δA 132.0, δX 41.3, JAX = 26.7 Hz. C40H40ClO4P3Ru (814.19):
calcd. C 59.01, H, 4.95, Cl 4.35%; found C 59.15, H 4.84, Cl 4.49%.
Scheme 6.
Conclusions
In this paper we report the preparation of mixed-ligands hy-
dride complexes [RuHCl(CO)(PPh3)2{P(OR)3}], which behave
as
a precursor for the synthesis of both hydrazine
[RuCl(CO)(κ1-NH2NHR1)(PPh3)2{P(OR)3}]BPh4 and diethyl-
cyanamide [RuCl(CO)(NϵCNEt2)(PPh3)2{P(OR)3}]BPh4 de-
rivatives.
1
2b: IR (KBr): ν˜ = (νCO) 1956 (s); (νRuH) 1903 (w) cm–1. H NMR
Experimental Section
(CD2Cl2, 20 °C): δ = 7.78–7.35 (m, 30 H, Ph), 3.64 (m, 6 H, CH2),
1.00 (t, 9 H, CH3), –5.74 (dt, JHP = 174.0, JHP = 20.5, 1 H, hydride)
ppm. 31P{1H} NMR (CD2Cl2, 20 °C): δ = AX2 spin syst, δA 130.1, δX
41.2, JAX = 26.7 Hz. C43H46ClO4P3Ru (856.27): calcd. C 60.32, H,
5.41, Cl 4.14%; found C 60.11, H 5.54, Cl 4.01%.
General Comments: The synthetic work was carried out in an appro-
priate atmosphere (Ar, N2) using standard Schlenk techniques or in an
inert-atmosphere glove box. Once isolated, the compounds were found
to be relatively stable in air. All solvents were dried with appropriate
drying agents, degassed on a vacuum line, and distilled into vacuum-
tight storage flasks. RuCl3·3H2O was a Pressure Chemical Co. (USA)
product, used as received. Phosphites P(OMe)3 and P(OEt)3 were Ald-
rich products and were purified by distillation in a nitrogen atmo-
sphere. Other reagents were purchased from commercial sources in the
highest available purity and used as received. Infrared spectra were
recorded with a Perkin–Elmer Spectrum-One FT-IR spectrophotome-
[RuCl(CO)(κ1-NH2NHR1)(PPh3)2{P(OR)3}]BPh4 (3, 4) [R1 = H (3),
Me (4); R = Me (a), Et (b)]: Triflic acid HOTf (0.11 mmol, 9.7 μL)
was added to
a
solution of the appropriate complex
[RuHCl(CO)(PPh3)2{P(OR)3}] (2) (0.1 mmol) in 5 mL of toluene
cooled to –196 °C. The reaction mixture was brought to 0 °C, stirred
for 40 min, and cooled again to –196 °C. An excess of the appropriate
hydrazine (0.22 mmol) in 5 mL of dichloromethane was added to the
reaction mixture, which was brought to 0 °C and stirred for 2 h. The
solvent was removed under reduced pressure to give an oil which was
treated with ethanol (2 mL) containing an excess of NaBPh4
(0.2 mmol, 68 mg). A pale-yellow solid slowly separated out, which
was filtered and crystallized from CH2Cl2 and EtOH (yield Ն 70%).
3b: IR (KBr): ν˜ = (νNH) 3353 (w), 3293 (m), 3267 (w); (νCO) 1982
(s) cm–1. 1H NMR (CD2Cl2, 20 °C): δ = 7.80–6.88 (m, 50 H, Ph),
3.59 (qnt, 6 H, CH2), 3.40 (br., 2 H, RuNH2), 2.95 (br., 2 H, NNH2),
1.03 (t, 9 H, CH3) ppm. 31P{1H} NMR (CD2Cl2, 20 °C): δ = AX2 spin
syst, δA 121.13, δX 35.73, JAX = 34.6 Hz. ΛM = 54.9 Ω–1·mol–1·cm2.
C67H69BClN2O4P3Ru (1206.53): calcd. C 66.70, H, 5.76, N 2.32, Cl
2.94%; found C 66.48, H 5.65, N, 2.43, Cl 3.06%. 4a: IR (KBr): ν˜ =
(νNH) 3326, 3275 (w); (νCO) 1971 (s) cm–1. 1H NMR (CD2Cl2,
20 °C): δ = 7.79–6.86 (m, 50 H, Ph), 3.34 (d, 9 H, CH3 phos), 3.11
(m, 1 H, NH), 2.55 (br., 2 H, NH2), 1.62 (d, 3 H, CH3N) ppm. 31P{1H}
1
ter. H and 31P{1H} NMR spectra were obtained with AVANCE 300
and AVANCE III 400 Bruker spectrometers at temperatures between
–90 and +30 °C, unless otherwise noted. 1H spectra are referred to
internal tetramethylsilane; 31P{1H} chemical shifts were reported with
respect to 85% H3PO4, with downfield shifts considered positive.
COSY, HMQC, and HMBC NMR experiments were performed with
standard programs. The iNMR software package[14] was used to pro-
cess NMR spectroscopic data. The conductivity of 10–3 mol·dm–3 solu-
tions of the complexes in CH3NO2 at 25 °C was measured with a
Radiometer CDM 83. Elemental analyses were determined in the
Microanalytical Laboratory of the Dipartimento di Scienze Farma-
ceutiche, University of Padova (Italy).
Synthesis of Complexes: The precursor compound [RuCl2(PPh3)3]
was prepared following the reported method.[15]
[RuHCl(CO)(PPh3)3] (1): In a 25-mL three-necked round-bottomed
flask were placed [RuCl2(PPh3)3] (0.25 g, 0.26 mmol), zinc dust
(60 mg, 0.9 mmol), and 15 mL ethanol. The reaction mixture was re-
fluxed for 3 h, filtered, and the volume was reduced to about 3 mL by
evaporation of the solvent under reduced pressure. A yellow solid
slowly separated out, which was filtered and crystallized from CH2Cl2
and ethanol; yield Ն 55%. IR (KBr): ν˜ = (νRuH) 2011 (w); (νCO)
NMR (CD2Cl2, 20 °C): δ = AX2 spin syst, δA 126.0, δX 32.23, JAX
=
33.1 Hz. ΛM = 55.1 Ω–1·mol–1·cm2. C65H65BClN2O4P3Ru (1178.48):
calcd. C 66.25, H, 5.56, N 2.38, Cl 3.01%; found C 66.07, H 5.42, N
2.30, Cl 3.16%. 4b: IR (KBr): ν˜ = (νNH) 3339, 3268 (w); (νCO) 1977
(s) cm–1. 1H NMR (CD2Cl2, 20 °C): δ = 7.77–6.87 (m, 50 H, Ph),
3.54 (m, 6 H, CH2), 3.01 (br., 1 H, NH), 2.50 (br., 2 H, NH2), 1.59
(d, 3 H, CH3N), 1.05 (t, 9 H, CH3) ppm. 31P{1H} NMR (CD2Cl2,
1
1925 (s) cm–1. H NMR (CD2Cl2, –60 °C): δ = 7.70–7.00 (m, 45 H,
Ph), –6.96 (dt, JHP = 10.3, JHP = 23,3, 1 H, hydride) ppm. 31P{1H}
20 °C): δ = AX2 spin syst, δA 119.8, δX 36.0, JAX = 34.0 Hz. ΛM
=
53.7 Ω–1·mol–1·cm2. C68H71BClN2O4P3Ru (1220.56): calcd. C 66.91,
NMR (CD2Cl2, 20 °C): δ = A2B spin syst, δA 41.6, δB 13.4, JAB
=
H, 5.86, N 2.30, Cl 2.90%; found C 66.75, H 5.98, N 2.18, Cl 3.04%.
16.4 Hz. C55H46ClOP3Ru (852.40): calcd. C 69.36, H 4.87, Cl 3.72%;
found C 69.61, H 4.78, Cl 3.58%.
[RuCl(CO)(NϵCNEt2)(PPh3)2{P(OR)3}]BPh4 (5) [R = Me (a), Et
[RuHCl(CO)(PPh3)2{P(OR)3}] (2) [R = Me (a), Et (b)]: Method 1: (b)]: This complex was prepared exactly like the related hydrazine
In 25-mL three-necked round-bottomed flask were placed derivatives 3 and 4 by treating [RuHCl(CO)(PPh3)2{P(OR)3}] (2) first
a
Z. Anorg. Allg. Chem. 2019, 688–693
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© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
with triflic acid and then with an excess of diethylcyanamide
Table 2. Crystal data and structure refinement for 2b.
NϵCNEt2. The yellow solid obtained was filtered and crystallized
from CH2Cl2 and EtOH; yield Ն 75%. 5a: IR (KBr): ν˜ = (νCN) 2273
2b
1
(m); (νCO) 1977 (s) cm–1. H NMR (CD2Cl2, 20 °C): δ = 7.81–6.87
Empirical formula
Formula weight
Temperature /K
Wavelength /Å
Crystal system
Space group
Unit cell dimensions:
a /Å
b /Å
C43H46ClO4P3Ru
856.23
293(2)
0.71073
monoclinic
P21/c
(m, 50 H, Ph), 3.31 (d, 9 H, CH3 phos), 2.52 (q, 6 H, CH2), 0.70 (t, 6
H, CH3 NEt) ppm. 31P{1H} NMR (CD2Cl2, 20 °C): δ = AX2 spin syst,
δA 124.64, δX 33.22, JAX = 32.81 Hz. ΛM = 54.6 Ω–1·mol–1·cm2.
C69H69BClN2O4P3Ru (1230.55): calcd. C 67.35, H, 5.65, N, 2.28, Cl
2.88%; found C 67.21, H 5.50, N, 2.37, Cl 2.99%. 5b: IR (KBr): ν˜ =
(νCN) 2278 (m); (νCO) 1975 (s) cm–1. 1H NMR (CD2Cl2, 20 °C):
δ = 7.83–6.86 (m, 50 H, Ph), 3.56 (m, 6 H, CH2 phos), 2.55 (q, 4 H,
CH2 NEt), 1.11 (t, 9 H, CH3 phos), 0.73 (t, 6 H, CH3 NEt) ppm.
31P{1H} NMR (CD2Cl2, 20 °C): δ = AX2 spin syst, δA 121.3, δX 35.8,
JAX = 34.7 Hz. ΛM = 55.0 Ω–1·mol–1·cm2. C72H75BClN2O4P3Ru
(1272.63): calcd. C 67.95, H, 5.94, N 2.20, Cl 2.79%; found C 67.73,
H 6.06, N, 2.08, Cl 2.66%.
17.771(3)
10.0406(14)
24.379(3)
110.371(3)
4078.1(10)
4
1.395
0.608
1768
c /Å
β /°
Volume /Å3
Z
Density (calculated) /Mg·m–3
Absorption coefficient /mm–1
F(000)
X-ray Data Collection and Refinement: Crystallographic data for
compound hydridechloridecarbonyl(triethoxyphosphine)[bis(triphenyl
phosphine)]ruthenium(II) (2b) were collected at room temperature
with a Bruker Smart 1000 CCD diffractometer at CACTI (Universid-
ade de Vigo) using graphite monochromated Mo-Kα radiation (λ =
0.71073 Å), and were corrected for Lorentz and polarization effects.
The software SMART[16] was used for collecting frames of data, in-
dexing reflections, and the determination of lattice parameters,
SAINT[16] for integration of intensity of reflections and scaling, and
SADABS[16] for scaling and empirical absorption correction. The crys-
tallographic treatment was performed with the Oscail program.[17] The
structure of the compound was solved by using the SHELXT pro-
gram[18] and refined by a full – matrix least – squares based on F2,
SHELXL program.[19] Non-hydrogen atoms were refined with aniso-
tropic displacement parameters. Hydrogen atoms were included in ide-
alized positions and refined with isotropic displacement parameters.
Five atoms on the ethoxy substituents in the phosphite ligands may be
split into two different positions, but this disorder was not modeled.
Details of crystal data and structural refinement are given in Table 2.
Crystal size /mm
Theta range for data collection
Index ranges
0.270ϫ0.200ϫ0.070
1.222 to 28.013°
–14 Յ h Յ 23
–13 Յ k Յ 13
–31 Յ l Յ 29
26626
9766 [Rint = 0.0780]
4687
0.991
Semi-empirical from equivalents
0.7456 and 0.7029
Full-matrix least-squares on F2
9766 / 0 / 476
1.007
R1 = 0.0542
Reflections collected
Independent reflections
Reflections observed (Ͼ2σ)
Data completeness
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
wR2 = 0.1134
R1 = 0.1542
wR2 = 0.1583
R indices (all data)
Largest diff. peak and hole /e·Å–3 1.193 and –0.879
M. Giacomello, Organometallics 2014, 33, 3570–3582; d) G. Al-
bertin, S. Antoniutti, A. Botter, J. Castro, J. Organomet. Chem.
2014, 774, 6–11; e) G. Albertin, S. Antoniutti, M. Bortoluzzi, J.
Castro, Inorg. Chim. Acta 2018, 470, 139–148; f) G. Albertin, S.
Antoniutti, J. Castro, V. Ganz, F. Sibilla, Dalton Trans. 2018, 47,
11658–11668; g) G. Albertin, S. Antoniutti, J. Castro, Chemis-
trySelect 2018, 3, 11054–11058; h) G. Albertin, S. Antoniutti, J.
Castro, G. Gasparetto, New J. Chem. 2019, 43, 2676–2686.
[3] N. Ahmad, J. J. Levison, S. D. Robinson, M. F. Uttley, Inorg.
Synth. 1974, 15, 45–64.
[4] W. J. Geary, Coord. Chem. Rev. 1971, 7, 81–112.
[5] a) L. J. Farrugia, ORTEP-3 for Windows - a version of ORTEP-
III with a Graphical User Interface (GUI), J. Appl. Crystallogr.
1997, 30, 565–565; b) POV-Ray v3.7 for Windows, Persistence of
Vision Pty. Ltd., 2016, Persistence of Vision Raytracer (Version
3.7) http://www.povray.org/documentation/.
Crystallographic data (excluding structure factors) for the structure in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
number CCDC-1899488 for 2b (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Acknowledgements
The financial support of MIUR - PRIN 2016 is gratefully acknowl-
edged. Thanks are also due to Daniela Baldan, of the Università Ca’
Foscari Venezia (Italy), for technical assistance.
[6] J. W. Gilje, R. Schmutzler, W. S. Sheldrick, V. Wray, Polyhedron
1983, 2, 603–606.
[7] a) G. Albertin, S. Antoniutti, M. Bortoluzzi, A. Botter, J. Castro,
Dalton Trans. 2015, 44, 3439–3446.
Keywords: Hydrides; Ruthenium; Carbonyl; Hydrazine; Di-
ethylcyanamide
[8] A. K. Widaman, N. P. Rath, E. B. Bauer, New J. Chem. 2011, 35,
2427–2434.
[9] S. K. Seetharaman, M.-C. Chung, U. Englich, K. Ruhlandt-Senge,
M. B. Sponsler, Inorg. Chem. 2007, 46, 561–567.
References
[1] G. Albertin, S. Antoniutti, L. Bonaldo, A. Botter, J. Castro, Inorg. [10] G. Albertin, S. Antoniutti, J. Castro, Organometallics 2010, 29,
Chem. 2013, 52, 2870–2879.
3808–3816.
[2] For our previous studies in thies field see: a) G. Albertin, S. An-
toniutti, J. Castro, Z. Anorg. Allg. Chem. 2014, 640, 136–139; b)
G. Albertin, S. Antoniutti, A. Caia, J. Castro, Dalton Trans. 2014,
43, 7314–7323; c) G. Albertin, S. Antoniutti, A. Botter, J. Castro,
[11] For diethylcyanamide complexes see: a) N. A. Bokach, V. Yu.
Kukushkin, Coord. Chem. Rev. 2013, 257, 2293–2316; b) G. Al-
bertin, S. Antoniutti, A. Caia, J. Castro, Z. Anorg. Allg. Chem.
2015, 641, 814–819; c) G. Albertin, S. Antoniutti, J. Castro,
Z. Anorg. Allg. Chem. 2019, 688–693
www.zaac.wiley-vch.de 692
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
ChemistrySelect 2018, 3, 11054–11058 and references cited
therein.
Field, H. L. Li, S. J. Dalgarno, Inorg. Chem. 2010, 49, 6214–
6221.
[14] G. Balacco, http://www.inmr.net/.
[15] G. P. Elliott, N. M. McAuley, W. R. Roper, Inorg. Synth. 1989,
26, 184–185.
[16] Bruker, APEX2, SMART, SAINT, Bruker AXS Inc., Madison, Wis-
consin, USA, 2016.
[17] P. McArdle, K. Gilligan, D. Cunningham, R. Dark, M. Mahon,
CrystEngComm 2004, 6, 303–309.
[18] G. M. Sheldrick, Acta Crystallogr., Sect. A 2015, 71, 3–8.
[12] a) J. R. Dilworth, Coord. Chem. Rev. 2017, 330, 53–94; b) B. T.
Heaton, C. Jacob, P. Page, Coord. Chem. Rev. 1996, 154, 193–
229; c) D. Sutton, Chem. Rev. 1993, 93, 995–1022; d) H. Kisch,
P. Holzmeier, Adv. Organomet. Chem. 1992, 34, 67–109; e) H.
Zollinger, Diazo Chemistry II, VCH, Weinheim, Germany, 1995.
[13] a) J. L. Crossland, D. R. Tyler, Coord. Chem. Rev. 2010, 254,
1883–1894; b) N. Hazari, Chem. Soc. Rev. 2010, 39, 4044–4056;
c) J. L. Crossland, L. N. Zakharov, D. R. Tyler, Inorg. Chem. [19] G. M. Sheldrick, Acta Crystallogr., Sect. C 2015, 71, 3–8.
2007, 46, 10476–10478; d) S. Dabb, B. Messerle, G. Otting, J.
Wagler, A. Willis, Chem. Eur. J. 2008, 14, 10058–10065; e) L. D.
Field, H. L. Li, A. M. Magill, Inorg. Chem. 2009, 48, 5–7; f) L. D.
Received: February 26, 2019
Published Online: April 25, 2019
Z. Anorg. Allg. Chem. 2019, 688–693
www.zaac.wiley-vch.de 693
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim