Heterobimetallic μ-nitrido complexes containing ruthenium(II) dithiocarbamate

Article abstract of DOI:10.1016/S0020-1693(00)00169-9

Interaction of [Ru(Co)H(Et₂dtc)with triflic acid (HOTf) afforded [Ru(Co)H(Et₂dtc)(PPh₃)₂(OTf) (1), which has been characterized by X-ray crystallography. The Ru-C, Ru-O, average Ru-S and average Ru-P distances in 1 are 1.811(5), 2.216(3), 2.433 and 2.423 ?, respectively. Reaction of 1 with amines L results in the formation of adducts trans-[Ru(CO)(Et₂dtc)(PPh₃)₂L](OTf) (L = N₂H₄ (2) and NH₂OH (3)). The Ru-C, Ru-N, average Ru-S and average Ru-P distance in 3 are 1.85(1), 2.179(8), 2.433 and 2.393, respectively; the Ru-N-O angle being 119.7(5)°. Treatment of 1 with [N(n)Bu₄][OsN(C₇H₆S₂)₂] ([C₇H₆S₂]^2- = 3,4-toluenedithiolate(2-)), and [ReN(Et₂dtc)₂] (Et₂dtc = N,N-diethyldithiocarbamate) gave the corresponding μ-nitrido complexes [Ru(CO)(Et₂dtc)(PPh₃)₂(NOsO₃)] (4), [Ru(CO)(Et₂dtc)(PPh₃)₂{NOs(C₇H₆S₂)₂}] (5) and [Ru(CO)(Et₂dtc)(PPh₃)₂{NRe(Et₂dtc)₂}] (6). The structures of complexes 4-6 have been established by X-ray crystallography. The Os-N and Ru-N distances, and Os-N-Ru angle in 4 are 1.719(7) and 2.075(7) ?, and 155.1(4)°, respectively. The Os-N and Ru-N distances and Os-N-Ru angle in 5 are 1.680(6) and 2.068(6) ?, and 166.2(3)°, respectively. The Re-N and Ru-N distances, and Re-N-Ru angle for 6 are 1.670(3) and 2.108(3) ?, and 170.9(2)°, respectively. The bond lengths and angles for these μ-nitrido complexes are indicative of asymmetric bridging mode of nitride, i.e. M≡N→ Ru(II) (M = Os(VIII), Os(VI), Re(V)). (C) 2000 Elsevier Science S.A.

Full text of DOI:10.1016/S0020-1693(00)00169-9

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Inorganica Chimica Acta 306 (2000) 184–192
Heterobimetallic m-nitrido complexes containing ruthenium(II)
dithiocarbamate
a,b
a,
a
a
Hegen Zheng , Wa-Hung Leung *, Joyce L.C. Chim , Willetta Lai ,
a
a
c
Chong-Ho Lam , Ian D. Williams , Wing-Tak Wong
a
Department of Chemistry, The Hong Kong Uni6ersity of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, PR China
b
Coordination Chemistry Institute and Department of Chemistry, Nanjing Uni6ersity, Nanjing 210093, PR China
c
Department of Chemistry, The Uni6ersity of Hong Kong, Pokfulam Road, Hong Kong, PR China
Received 21 October 1999; accepted 17 April 2000
Abstract
Interaction of [Ru(Co)H(Et dtc)with triflic acid (HOTf) afforded [Ru(Co)H(Et dtc)(PPh ) (OTf) (1), which has been character-
2
2
3 2
ized by X-ray crystallography. The RuꢀC, RuꢀO, average RuꢀS and average RuꢀP distances in 1 are 1.811(5), 2.216(3), 2.433 and
.423 A, respectively. Reaction of 1 with amines L results in the formation of adducts trans-[Ru(CO)(Et dtc)(PPh ) L](OTf)
L=N H (2) and NH OH (3)). The RuꢀC, RuꢀN, average RuꢀS and average RuꢀP distance in 3 are 1.85(1), 2.179(8), 2.433 and
2
(
2
,
2
3 2
2−
2
4
2
n
.393, respectively; the RuꢀNꢀO angle being 119.7(5)°. Treatment of 1 with [N Bu ][OsN(C H S ) ] ([C H S ] =3,4-
4
7
6
2 2
7
6 2
toluenedithiolate(2−)), and [ReN(Et dtc) ] (Et dtc=N,N-diethyldithiocarbamate) gave the corresponding m-nitrido complexes
2
2
2
[
Ru(CO)(Et dtc)(PPh ) (NOsO )] (4), [Ru(CO)(Et dtc)(PPh ) {NOs(C H S ) }] (5) and [Ru(CO)(Et dtc)(PPh ) {NRe(Et dtc) }]
2 3 2 3 2 3 2 7 6 2 2 2 3 2 2 2
(
6). The structures of complexes 4–6 have been established by X-ray crystallography. The OsꢀN and RuꢀN distances, and
, and 155.1(4)°, respectively. The OsꢀN and RuꢀN distances and OsꢀNꢀRu angle
, and 166.2(3)°, respectively. The ReꢀN and RuꢀN distances, and ReꢀNꢀRu angle for 6 are
OsꢀNꢀRu angle in 4 are 1.719(7) and 2.075(7) A
in 5 are 1.680(6) and 2.068(6) A
.670(3) and 2.108(3) A, and 170.9(2)°, respectively. The bond lengths and angles for these m-nitrido complexes are indicative of
,
,
,
1
asymmetric bridging mode of nitride, i.e. MꢁN“Ru(II) (M=Os(VIII), Os(VI), Re(V)). © 2000 Elsevier Science S.A. All rights
reserved.
Keywords: Crystal structures; Ruthenium complexes; Nitrido complexes; Heterobimetallic complexes
1
. Introduction
The bonding in these osmium m-nitrido complexes con-
10 8
taining d - and d -configured M are best described as
OsꢁN“M, consisting of OsꢁN triple bond and
OsNꢀM donor–acceptor type interaction [5], whereas
RuꢀN multiple bond character was also noted in
m-Nitrido-bridged dimetallic complexes are of interest
because they are believed to play important roles in
metal-centered nitrogen atom transfer reactions [1–4].
Previously we reported that m-nitrido osmium com-
plexes can be prepared conveniently by metathesis of
anionic nitridoꢀosmium(VIII) or nitridoꢀosmium(VI)
complexes with appropriate metal triflates including
[
Ru(OEP)(NO)(NOsO )] [7]. To further probe the influ-
3
ence of M on the bonding mode in OsNM complexes,
we set out to prepare bimetallic nitrido complexes
containing other Ru(II) fragments. [Ru(CO)(Et dtc)-
2
1
0
8
d -configured [Au(PPh )(OTf)] and d -configured
3
(
PPh ) (OTf)] (Et dtc=N,N-diethyldithiocarbamate) is
3 2 2
6
[Pt(PR ) (OTf) ], [Ir(CO)(PPh ) (OTf)] [5,6] and d -
3 2 2 3 2
chosen to be
a
nitride acceptor because the
configured
[Ru(OEP)(NO)(OTf)]
(OTf=triflate;
[
Ru(CO)(R dtc)(PPh ) ] cores (R=Me or Et; n=1 or
2
3 n
H OEP=2,3,7,8,12,13,17,18-octaethylporphyrin) [7].
2
2
) are known to form stable complexes with p-donor
ligands such as thiophenolate, polysulfides [8] and N-
donor ligands such as amines [9] and tosylamide [10].
*
Corresponding author. Tel.: +852-2358 7360; fax: +852-2358
594.
E-mail address: chleung@ust.hk (W.-H. Leung).
1
We here report the reactions of [Ru(CO)(Et dtc)-
2
0020-1693/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0020-1693(00)00169-9

H. Zheng et al. / Inorganica Chimica Acta 306 (2000) 184–192
185
(
PPh ) (OTf)] with hydrazine, hydroxylamine and metal
2.2.2. [Ru(CO)(Et dtc)(PPh ) (NH NH )](OTf) (2)
3
2
2
3 2
2
2
nitrides and the isolation of the respective Ru(II) amine
To a solution of 1 (0.10 g, 0.11 mmol) in CH Cl (20
2
2
and m-nitrido complexes.
ml) was added hydrazine hydrate (0.1 ml) and the
reaction mixture was stirred at room temperature for 1
h. The solvent was then pumped off and the residue
was washed with Et O. Recrystallization from
2
. Experimental
2
CH Cl ꢀEt O afforded yellow crystals. Yield: 0.08 g
2
2
2
(
75%). Anal. Calc. for C H F N O P RuS ·CH Cl :
2
.1. General
43 44 3 3 4 2 3 2 2
C, 49.5; H, 4.3; N, 3.9. Found: C, 48.9; H, 4.5; N, 3.7%.
1
H NMR (CDCl ): l 1.20 (t, 6H, CH CH ), 3.47–3.78
All manipulations were carried out under nitrogen
3
2
3
(
2
m, 4H, CH CH ), 3.42 (s br, 2H, N H ), 4.48 (s br,
using standard Schlenk techniques. Solvents were
purified and distilled prior to use. NMR spectra were
recorded on a Bruker ALX 300 spectrometer. Chemical
2 3 2 4
31
1
H, N H ), 7.27−7.46 (m, 30H, phenyl H). P{ H}
2 4
−
1
NMR (CDCl ): l 38.76. IR (Nujol): w(cm ), 1976
3
[
w(CꢁO)]; 3335, 3315 [w(NH )].
shifts (l, ppm) were reported with reference to SiMe
2
4
1
31
(
H) and H PO ( P). Infrared spectra (Nujol) were
3 4
2
.2.3. [Ru(CO)(Et dtc)(PPh ) (NH OH)](OTf) (3)
recorded on a Perkin–Elmer 16 PC FTIR spectropho-
tometer. Mass spectra were obtained on a Finnigan
TSQ-7000 spectrometer. Cyclic voltammetry was per-
formed with a Princeton Applied Research (PAR)
Model 273A potentiostat. The working and reference
2
3 2
2
To a solution of 1 (0.06 g, 0.06 mmol) in CH Cl (20
2
2
ml) was added 1 equiv. of hydroxylamine and the
reaction mixture was stirred at room temperature for 2
h. The solvent was pumped off and the residue was
recrystallised from CH Cl –hexane to afford yellow
electrodes are glassy carbon and AgꢀAgNO (0.1 M in
2
2
3
crystals. Yield: 0.05 g, 85%. Anal. Calc. for C H F -
acetonitrile) electrodes, respectively. Potentials were re-
ported with reference to the ferrocenium–ferrocene
couple. Elemental analyses were performed by Medac
Ltd, Surrey, UK.
43 43 3
N O P RuS ·CH Cl : C, 49.4; H, 4.2; N, 2.6. Found: C,
2
5
2
3
2
2
1
4
9.3; H, 4.1; N, 2.6%. H NMR (CDCl ): l 1.16 (t, 6H,
3
CH CH ), 3.62 (m, 4H, CH CH ), 6.14 (s br, 2H,
2
3
2
3
NH ), 6.99 (s br, 1H, OH), 7.28–7.40 (m, 30H, phenyl
The compounds [Ru(CO)(H)(Et dtc)(PPh ) ] [11],
2
2
3 2
31
1
n
n
H). P{ H} NMR (CDCl ): l 38.73. IR (Nujol):
[N Bu ][OsO N]
[12],
[N Bu ][OsN(C H S ) ]
3
4
3
4
7
6 2 2
−
1
2
−
w(cm ), 1976 [w(CꢀO)]; 3260 [w(NH )]; 3500 br
2
(
[C H S ] =3,4-toluenedithiolate(2−)] [6,13] and
7
6 2
[w(OH)].
[ReN(Et dtc) ] [14] were synthesized according to the
2 2
literature methods. The hydrogen atom labelling
2
6 2
−
2.2.4. [Ru(CO)(Et dtc)(PPh ) (NOsO )] (4)
scheme for C H S
is shown below.
2
3 2
3
7
To a solution of 1 (0.10 g, 0.11 mmol) in CH Cl (15
2
2
n
ml) was added 1 equiv. of [N Bu ][NOsO ] (0.05 g, 0.11
4
3
mmol). The reaction mixture was stirred at room tem-
perature for 1 h. The solvent was then pumped off in
vacuo, and the orange residue was recrystallized from
CH Cl –hexane to afford dark orange crystals. Yield:
2
2
0
.07 g (60%) Anal. Calc. for C H N O OsP RuS : C,
42 40 2 4 2 2
4
8.5; H, 3.9; N, 2.6. Found: C, 47.9; H, 3.8; N, 2.7%.
1
2
.2. Synthesis
H NMR (CDCl ): l 1.24 (t, 6H, CH CH ), 3.60 (q,
3
3
2
31
1
4
H, CH CH ), 7.29–7.36 (m, 30H, phenyl H). P{ H}
3 2
−
1
2
0
.2.1. [Ru(CO)(Et dtc)(PPh ) (OTf)] (1)
NMR (CDCl ): l 39.22 (s) IR (Nujol): w(cm ), 882,
902 [w(OsꢂO)], 1092 [w(OsꢁN)], 1970 [w(CꢁO)].
2
3 2
3
To a solution of [Ru(CO)(H)(Et dtc)(PPh ) ] (0.10 g,
.12 mmol) in CH Cl (20 ml) was added excess triflic
2
3 2
2
2
acid (0.2 ml of a 1 M solution in CH Cl ) at 0°C. The
2.2.5. [Ru(CO)(Et dtc)(PPh ) {NOs(C H S ) }] (5)
2
2
2
3 2
7
6 2 2
reaction mixture was warmed to room temperature and
was stirred overnight. The solvent was then pumped off
To a solution of 1 (0.093 g, 0.1 mmol) in CH Cl (10
2
2
n
ml) was added 1 equiv. of [N Bu ][OsN(C H S ) ]
4
7
6 2 2
and the residue was washed with Et O. Recrystalliza-
(0.075 g, 0.1 mmol) and the mixture was stirred at room
temperature for 2 h. The solvent was pumped off and
2
tion from CH Cl –hexane afforded pale yellow crys-
2
2
tals. Yield: 0.023
g
(20%). Anal. Calc. for
the dark residue washed with hexane and Et O. Recrys-
2
C H F NO P RuS : C, 54.3; H, 4.2; N, 1.5. Found:
tallization from CH Cl –hexane afforded dark yellow
4
3
40
3
4
2
3
2
2
1
C, 54.6; H, 4.3; N, 1.5%. H NMR (CDCl ): l 1.20 (t,
crystals. Yield: 0.065
g (50%). Anal. Calc. for
3
6
3
H, CH CH ), 3.65 (q, 4H, CH CH ), 7.24−7.37 (m,
C H N OOsP RuS : C, 51.1; H, 4.1; N, 2.1. Found:
2 3 2 3
1
56 52
2
2
6
3
1
1
0H, phenyl H). P{ H} NMR (CDCl ): l 38.24 (s).
C, 51.0; H, 4.0; N, 2.1%. H NMR (CDCl ): l 1.33
3
3
−
1
IR (Nujol): w(cm ), 1950 [w(CꢁO)]; 1032, 1232, 1324
(overlapping t, 6H, CH ), 2.35 (s, 6H, CH of C H S ),
3
3
7
6 2
[
w(SꢂO)].
3.47–3.66 (m, 4H, CH ), 6.74 (d, J=7.9 Hz, 2H, H ),
2 b

186
H. Zheng et al. / Inorganica Chimica Acta 306 (2000) 184–192
3
1
1
1
7
.42 (s, 2H, H ), 7.50 (d, J=7.9 Hz, 2H, H ). P { H}
complex 3, an approximation to absorption correction
c
a
−
NMR (CDCl ): l 33.45 (s). IR (Nujol): w(cm ), 1974
by inter-image scaling was also applied. The large resid-
3
−
3
[
w(CO)].
.2.6. [Ru(CO)(Et dtc)(PPh ) {NRe(Et dtc) }](OTf) (6)
ual maximum (+2.9 e A
A
,
,
) and minimum (−3.0 e
) electron density in compound 4 are 0.92 and 0.79
,
A from the Os atom, respectively. No peaks of chemical
−
3
2
2
3 2
2
2
To a solution of 1 (0.10 g, 0.11 mmol) in CH Cl (15
significance remain in the structure. All the structures
were solved by direct methods and refined by full-ma-
trix least-squares procedures. Calculations were per-
formed using the SHELXL [15] (for complexes 1 and
4–6) and TEXSAN (for complex 3) [16] crystallographic
packages. The disorder of the coordinated triflate in 1
appears to be 90:10. Whilst a discernible peak may be
found for S(3A), which has similar geometry to O(2)
and O(3), the 10% occupancy peaks for the rest of
group are too small to be modelled. The presence of the
disorder thus increases the thermal parameters of the
remaining atoms of the group since they must still be
refined with full occupancy factors. For 5, the disorder
for the methyl group in the toluenedithiolate ligands is
not constrained to be 50:50 by crystallographic symme-
try. The ring C(77) position has 60:40 disorder and
C(87) 55:45. This was modelled by holding the two
thermal parameters equivalent and refining the site
occupancy. The site occupancies were then rounded off
and fixed, and separate isotropic thermal parameters
refined (all U’s are in the range of 0.13–0.14). The
C(77) and C(87) groups of the neighbouring molecules
are not in contact, so the two disorders were treated
independently. The disorder for the phenyl groups in 6
2
2
ml) was added 1 equiv. of [ReN(Et dtc) ] (0.05 g, 0.11
2
2
mmol). The yellow reaction mixture was stirred at room
temperature overnight. The solvent was then pumped
off in vacuo, and the yellow residue was recrystallized
from CH Cl –hexane to afford yellow crystals, which
2
2
were suitable for X-ray diffraction study. Yield: 0.06 g
(
38%). Anal. Calc. for C H F N O P ReRuS : C,
53 60 3 4 4 2 7
4
4.0; H, 4.2; N, 3.9. Found: C, 42.7; H, 4.1; N, 3.8%.
1
H NMR (CDCl ): l 1.25–1.40 (m, 18H, CH CH ),
3
3
2
3
.63−3.92 (m, 12H, CH CH ), 7.20–7.43 (m, 30H,
3 2
3
1
1
phenyl H). P{ H} NMR (CDCl ): l 35.47 (s). IR
3
−
1
(
Nujol): w(cm ), 1970 [w(CO)].
2.3. X-ray crystallography
A summary of pertinent crystal data and experimen-
tal details for complexes 1, 3, 4, 5 and 6 are listed in
Table 1. Intensity data were collected on a Siemens P4
diffractometer (for 1, 4, 5 and 6) and a MAR research
image-plate diffractometer (for 3) at room temperature
using the graphite-monochromated Mo Ka radiation (u
0
.71073 A). The absorption corrections for complexes 1
,
and 4–6 are semi-empirical based on psi-scan data. For
Table 1
Crystal data and experimental details for [Ru(CO)(Et dtc)(PPh )(OTf)] (1), [Ru(CO)(Et dtc)(PPh ) (NH2OH)](OTf) (3), [Ru(CO)(Et dtc)-
2
3
2
3 2
2
(
PPh ) (NOsO )] (4), [Ru(CO)(Et dtc)(PPh ) {NOs(C H S )}] (5) and [Ru(CO)(Et dtc)(PPh ) {NRe(Et dtc) }](OTf) (6)
3 2 3 2 3 2 7 6 2 2 3 2 2 2
1
3
4
5
6
Empirical formula
Formula weight
Crystal system
C H F NO P RuS C H F N O P RuS C H N O OsP S Ru C H N OOsP RuS C H F N O P ReRuS
43 40 3 4 2 3 43 43 3 2 5 2 3 42 40 2 4 2 2 56 52 2 2 6 53 60 3 4 4 2 7
950.95
984.02
1054.09
1314.57
1447.68
monoclinic
10.372(4)
23.670(9)
17.785(6)
triclinic
monoclinic
10.373(1)
22.949(1)
17.521(1)
monoclinic
13.217(1)
22.028(2)
19.985(2)
triclinic
a (A
,
)
)
)
11.348(1)
14.773(1)
16.395(1)
106.36(2)
101.57(2)
102.84(2)
2467.5(7)
11.4980(1)
16.286(2)
16.320(3)
92.270(1)
93.450(1)
97.140(1)
3023.4(7)
b (A
,
c (A
,
h (°)
i (°)
k (°)
90.26(2)
90.330(1)
107.49(1)
V (A
,
3)
4366(3)
4170.8(5)
5549.5(9)
Space group
Z
P2 /n (no. 14)
4
P1
2
(
(no. 2)
P2 /n (no. 14)
4
P2 /n (no. 14)
4
P1 (no. 2)
(
2
1
1
1
Dcalc (g cm−3)
Temperature (K)
F(000)
1.447
293
1.324
298
1.679
293
1.573
293
1.590
293
1944
6.3
10 504
1008
5.62
8578
2080
36.25
10 371
2624
28.33
9908
1452
25.99
14 341
v(Mo Ka) (cm−1)
Total reflections
Independent reflections 8546 (Rint=0.0481)
8460 (Rint=0.0312)
9448 (Rint=0.0443) 13 677 (Rint=0.0315)
Observed reflections
7334 [I\1.5|(I)]
R1 (F \2|(F ))
wR2 (all data)
Goodness-of-fit
0.0489
0.1345
1.020
0.090
0.144
5.39
0.0666
0.1905
1.067
0.0503
0.1113
1.018
0.0353
0.0951
0.999
o
o
a
a
Rw refined on F.

H. Zheng et al. / Inorganica Chimica Acta 306 (2000) 184–192
187
compound, indicating that the coordinated triflate is a
rather weak donor ligand. Fig. 1 shows the molecular
structure of 1; selected bond lengths and angles are
listed in Table 2. The geometry around Ru is pseudo-
octahedral with the triflate trans to the carbonyl. This
structure is different from that for a related compound
−
[
Ru(SH)(CO)(Et dtc)(PPh ) ], in which the HS and
2 3 2
CO ligands are mutually cis and the two PPh mutually
3
trans [17]. The average RuꢀP distance in 1 (2.423 A
,
) is
slightly longer than that in [Ru(SH)(CO)(Et dtc)-
2
(
2
[
PPh ) ] (2.381 A
,
) [17]. The average RuꢀS distance of
3
2
.433 A is typical for Ru(II) dithiocarbamte complexes
,
9,10].
.2. Amine adducts of 1
Complex 1 was found to react with N-donor ligands
3
to give the corresponding adducts of Ru(II) dithiocar-
bamate (Scheme 1).
Thus, treatment of 1 with hydrazine hydrate afforded
Fig. 1. Perspective view of [Ru(CO)(Et dtc)(PPh ) (OTf)] (1). Phenyl
rings of PPh3 are omitted for clarity
2
3 2
the
hydrazine
adduct
[Ru(CO)(Et dtc)(PPh ) -
2 3 2
(
N H )](OTf) (2). The IR spectrum for 2 shows w(NꢀH)
2
4
Table 2
Selected bond lengths (A
−
1
1
,
)
and angles (°) for trans-[Ru(CO)-
at 3315 and 3335 cm . The H NMR spectrum of 2
shows two broad singlets at l 3.42 and 4.48, assignable
to the amino protons. The IR w(CO) for 2 of 1976
cm is higher than that for 1 due to cationic nature of
the complex.
(
Et dtc)(PPh ) (OTf)] (1)
2
3 2
RuꢀP(1)
RuꢀS(1)
RuꢀO(2)
O(1)ꢀC(1)
2.441(1)
RuꢀP(2)
RuꢀS(2)
RuꢀC(1)
2.404(1)
2.434(2)
1.811(5)
−1
2.431(2)
2.216(3)
1.153(5)
Similarly, reaction of 1 with hydroxylamine hydrate
afforded the Ru(II) hydroxylamine adduct [Ru(CO)-
P(1)ꢀRuꢀP(2)
P(2)ꢀRuꢀS(1)
P(2)ꢀRuꢀS(2)
P(1)ꢀRuꢀO(2)
S(1)ꢀRuꢀO(2)
P(1)ꢀRuꢀC(1)
S(1)ꢀRuꢀC(1)
RuꢀC(1)ꢀO(1)
102.4(1)
164.2(1)
92.1(1)
93.1(1)
90.4(1)
91.0(1)
86.1(2)
175.5(4)
P(1)ꢀRuꢀS(1)
P(1)ꢀRuꢀS(2)
S(1)ꢀRuꢀS(2)
P(2)ꢀRuꢀO(2)
S(2)ꢀRuꢀO(2)
P(2)ꢀRuꢀC(1)
S(2)ꢀRuꢀC(1)
93.5(1)
165.6(1)
72.1(1)
88.7(1)
87.5(1)
93.5(2)
87.7(1)
(
Et dtc)(PPh ) (NH OH)](OTf) (3). The IR spectrum of
2
3 2
2
3 shows w(NH) at 3260 along with w(OH) at 3500
cm . In the H NMR spectrum of 3, the amino and
hydroxyl protons appear as broad singlets at l 6.14 and
−
1
1
6
.99, respectively. The structure of 3 has been unam-
biguously established by X-ray crystallography. Fig. 2
shows a diagram of the molecule; selected bond lengths
and angles are given in Table 3. The geometry around
Ru is distorted octahedral with the hydroxylamine trans
to CO. The average RuꢀS, average RuꢀP and RuꢀC
distances (2.433, 2.393, and 1.85(1) A
similar to those in 1. The RuꢀN distance of 2.179(8) A
is slightly shorter than those in {[Ru(Me dtc)(CO)-
is difficult to model but appears to be 80:20. A figure
showing the disorder is added to the supplementary
material.
,
, respectively) are
,
2
(
PPh )] (m-S )(m-N H )} (2.222(8) and 2.228(8) A
,
) [9].
is similar to that in
Re(CO) (PPh ) (NH OH)](OTf) (1.422(5) A) [18]. The
3
. Results and discussion
3
2
4
2
4
The NꢀO distance of 1.45(1) A
[
,
,
3.1. Synthesis of [Ru(CO)(Et dtc)(PPh ) (OTf)]
3
3 2
2
2
3 2
RuꢀNꢀO angle of 119.7(5)° is larger than the ideal
tetrahedral value (109.5°). A similar bond angle has
been found for [Re(CO) (PPh ) (NH OH)](OTf)
The triflate compound [Ru(CO)(Et dtc)(PPh ) (OTf)]
2
3 2
(
1) was made in high yield by reaction of triflic acid
3
3 2
2
(
ReꢀNꢀO angle=116.4(3)°) [18].
with [Ru(CO)(Et dtc)(PPh ) (H)], isolated as air-stable
2
3 2
cream coloured crystals Eq. (1)
3
.3. Heterobimetallic nitrido complexes with Ru
[
Ru(CO)(H)(Et dtc)(PPh ) ]+HOTf
dithiocarbamate
2
3 2
“
[Ru(CO)(Et dtc)(PPh ) (OTf)]+H
(1)
2
3 2
2
Complex 1 was also found to react with metal ni-
−
1
The w(CO) for 1 occurs at 1950 cm , which is
trides to give binuclear nitrido complexes. Thus, treat-
n
considerably lower than that for the starting hydride
ment of
1
with [N Bu ][OsO N] afforded the
4
3

188
H. Zheng et al. / Inorganica Chimica Acta 306 (2000) 184–192
−
−1
Ru(II)NOs(VIII) complex [Ru(CO)(Et dtc)(PPh ) -
which is higher than that for [OsO N] (1023 cm
)
2
3 2
3
(
NOsO )] (4). Like the reported MNOs(VIII) [M=
[12]. The structure of 4 has been unambiguously estab-
lished by X-ray crystallography. Fig. 3 shows a perspec-
tive view of the molecule; selected bond lengths and
angles are listed in Table 4. The geometry around Ru is
3
Au(I), Pt(II), Ir(I)] complexes [5,6], the w(Os=O) for 4
−
1
(
882 and 902 cm ) are higher than those for
−
−1
[OsO N] (858 and 890 cm ) [12], suggesting that the
3
OsꢂO bonds are strengthened on formation of nitride
pseduo-octahedral with the [NOsO ] group trans to the
carbonyl. The OsꢀN and average OsꢀO distances for 4
3
−
1
bridge. The w (OsꢁNꢀRu) was found at 1070 cm
,
as
Scheme 1.
Fig. 2. Perspective view of [Ru(CO)(Et dtc)(PPh ) (NH OH)](OTf) (3).
2
3 2
2

H. Zheng et al. / Inorganica Chimica Acta 306 (2000) 184–192
189
Table 3
Selected bond lengths (A
PPh ) )(NH OH)](OTf) (3)
Table 4
Selected bond lengths (A
(PPh ) (NOsO )] (4)
3 2 3
,
) and angles (°) for trans-[Ru(CO(Et dtc)-
,
) and angles (°) for [Ru(CO)(Et dtc)-
2
2
(
3
2
2
Ru(1)ꢀS(1)
Ru(1)ꢀP(1)
Ru(1)ꢀN(1)
C(1)ꢀO(1)
2.434(3)
2.403(2)
2.179(8)
1.15(1)
Ru(1)ꢀS(2)
Ru(1)ꢀP(2)
Ru(1)ꢀC(1)
N(1)ꢀO(2)
2.431(3)
2.382(2)
1.85(1)
1.45(1)
Os(1)ꢀO(2)
Os(1)ꢀO(4)
Ru(1)ꢀP(1)
Ru(1)ꢀS(1)
Ru(1)ꢀN(1)
O(1)ꢀC(1)
1.712(10)
1.675(13)
2.383(2)
2.433(3)
2.075(7)
1.135(12)
Os(1)ꢀO(3)
Os(1)ꢀN(1)
Ru(1)ꢀP(2)
Ru(1)ꢀS(2)
Ru(1)ꢀC(1)
1.661(13)
1.719(7)
2.382(2)
2.424(3)
1.849(9)
S(1)ꢀRu(1)ꢀS(2)
S(1)ꢀRu(1)ꢀP(2)
S(1)ꢀRu(1)ꢀC(1)
S(2)ꢀRu(1)ꢀP(2)
S(2)ꢀRu(1)ꢀC(1)
P(1)ꢀRu(1)ꢀN(1)
P(2)ꢀRu(1)ꢀN(1)
72.21(9)
163.68(9)
90.5(3)
91.48(9)
91.9(3)
S(1)ꢀRu(1)ꢀP(1)
S(1)ꢀRu(1)ꢀN(1)
S(2)ꢀRu(1)ꢀP(1)
S(2)ꢀRu(1)ꢀN(1)
P(1)ꢀRu(1)ꢀP(2)
P(1)ꢀRu(1)ꢀC(1)
P(2)ꢀRu(1)ꢀC(1)
Ru(1)ꢀN(1)ꢀO(2)
90.72(8)
85.3(2)
162.82(9)
80.6(2)
105.56(9)
90.1(3)
90.5(3)
O(2)ꢀOs(1)ꢀO(3) 112.1(6)
O(3)ꢀOs(1)ꢀO(4) 112.3(8)
O(3)ꢀOs(1)ꢀN(1) 109.3(5)
P(1)ꢀRu(1)ꢀP(2) 102.3(1)
P(2)ꢀRu(1)ꢀS(1)
P(2)ꢀRu(1)ꢀS(2) 164.0(1)
P(1)ꢀRu(1)ꢀN(1)
S(1)ꢀRu(1)ꢀN(1)
P(1)ꢀRu(1)ꢀC(1)
S(1)ꢀRu(1)ꢀC(1)
N(1)ꢀRu(1)ꢀC(1) 171.6(4)
Ru(1)ꢀC(1)ꢀO(1) 171.2(9)
O(2)ꢀOs(1)ꢀO(4)
O(2)ꢀOs(1)ꢀN(1)
O(4)ꢀOs(1)ꢀN(1)
P(1)ꢀRu(1)ꢀS(1)
P(1)ꢀRu(1)ꢀS(2)
S(1)ꢀRu(1)ꢀS(2)
P(2)ꢀRu(1)ꢀN(1)
S(2)ꢀRu(1)ꢀN(1)
P(2)ꢀRu(1)ꢀC(1)
S(2)ꢀRu(1)ꢀC(1)
Os(1)ꢀN(1)ꢀRu(1)
104.8(7)
109.2(4)
109.0(5)
165.6(1)
93.6(1)
72.1(1)
94.4(2)
85.7(2)
92.3(3)
86.5(3)
155.1(4)
96.4(2)
91.8(2)
92.0(1)
N(1)ꢀRu(1)ꢀC(1) 172.3(4)
Ru(1)ꢀC(1)ꢀO(1) 176.0(10)
119.7(5)
91.0(2)
87.2(2)
92.6(3)
87.5(3)
(
1.719(7) and 1.682 A
,
, respectively) are similar to those
in [Au(PPh )(NOsO )] [5]. The RuꢀN distance for 4 of
3
3
2
.075(7) A
longer than those for typical m-nitridoruthenium com-
plexes, e.g. K [Ru NCl (H O) ] (1.718(3) A) [19],
Ru N(en) ]Cl (en=1,2-diaminoethane, 1.742(1) A
,
is comparable to that in 3 but considerably
,
Like [Au(PPh )(NOsO )] [5] and [Ru(NO)(OEP)-
3 3
3
2
8
2
2
[
[
1
,
)
(NOsO )] [7], no reactions between 4 and alkenes such
2
5
5
3
20],
.744(2) A
21], which contain symmetric RuꢂNꢂRu bridges. The
RuꢀNꢀOs linkage in 4 is slightly bent with an angle of
55.1(4)°, which is larger than that for [Ru(OEP)-
NO)(NOsO )] (138.4(8)°) [7]. These structural data are
[Ru N(bpy) Cl (H O)]
(bpy=2,2%-bipyridine,
as styrene were observed.
Treatment of 1 with [N Bu ][OsN(C H S ) ] afforded
2
2
5
2
n
,
), and (H O )[Ru N(bpy) Cl ] (1.734(4) A
,
)
5
2
2
2
6
4
7
6 2 2
[
the
Ru(II)NOs(VI)
complex
[Ru(CO)(Et dtc)-
2
(PPh ) {NOs(C H S ) }] 5. The molecular structure of
3
2
7
6 2 2
1
(
5 is shown in Fig. 4; selected bond lengths and angles
are listed in Table 5. The geometry around Os is
distorted square pyramidal with Os situated at ca. 0.70
3
indicative of the OsꢁNꢀRu bonding mode, consisting of
an OsꢁN triple bond and OsN“Ru dative bond. This
bonding picture is in agreement with IR data: the
w(CO) for 4 (1970 cm ) is higher than that for the
amide complex [Ru(CO)(Et dtc)(PPh ) (NTs)] (Ts=to-
A above the S plane. The Os-to-S plane displacement
,
4 4
for 5 is similar to that for a related Os–Ir bimetallic
complex [Ir(CO)(PPh ) {NOs(C H S ) }] (0.69 A) [6].
] and average OsꢀS (2.305 A
distances and average NꢀOsꢀS angle (107.6°) are simi-
−
1
,
3
2
7
6 2 2
The OsꢀN [1.680(6) A
,
,
)
2
3 2
−
1
syl, 1936 cm ) [10] but similar to those for 2 and 3.
Fig. 3. Perspective view of [Ru(CO)(Et dtc)(PPh ) (NOsO )] (4). Phenyl rings of PPh are omitted for clarity.
2
3 2
3
3

190
H. Zheng et al. / Inorganica Chimica Acta 306 (2000) 184–192
Fig. 4. Perspective view of [Ru(CO)(Et dtc)(PPh ) {NOs(C H S ) }] (5). Phenyl rings of PPh are omitted for clarity.
2
3 2
7
6
2 2
3
−
lar to those for [OsN(C H S ) ] (1.65 and 2.323 A
1
,
and
nitrido complexes containing the [Ru(CO)(Et dtc)-
6
4
2 2
2
07.2°, respectively) [13], suggesting that the OsꢁN
(PPh ) ] moiety. The crystal structures for these m-ni-
3
2
−
triple bond in [OsN(C H S ) ] is not significantly per-
trido-Ru(II) complexes suggest asymmetric bridging
mode of nitride, i.e. MꢁN“Ru. On the basis of the IR
CO stretching frequencies, there is no evidence for
nitride-to-Ru p interaction in these complexes. The
donor strength of the bridging nitride ligand in this
binuclear complex was found to be similar to that for
hydrazine or hydroxylamine. The RuꢀNꢀM linkage in
these complexes are roughly linear (RuꢀNꢀM angle
ranging from 155.1(4) to 170.9(2)°). The slight bending
of RuꢀNꢀM may be due to steric reasons and/or elec-
tron factors, which have yet to be explored.
6
4 2 2
turbed on coordination to Ru. The long RuꢀN distance
2.068(6) A) together with the approximately linear
OsꢀNꢀRu linkage (166.2(3)°) indicate that the interac-
tion between Ru and nitride in 5 is also of donor
acceptor type. Accordingly, the IR CO stretching mode
occurs at a quite high energy (1974 cm ). The
w (OsꢁNꢀRu) was not assigned due to the presence of
ligand bands in the 1000–1200 cm
(
,
−
1
as
−
1
region. The cyclic
voltammogram of 5 in CH Cl features a reversible
2
2
couple (i /i ꢁ1 and scan-rate independent) at ca. 0.38
a
c
V versus ferrocenium–ferrocene, which is tentatively
assigned as the Os(VII)ꢀOs(VI) couple. The Os(-
Table 5
Selected bond lengths and angles for {Ru(CO)(Et dtc)-
2
VII)ꢀOs(VI) potential for 5 is identical with that for
(
PPh ) [NOs(C H S ) ]} (5)
3 2 7 6 2 2
−
[
OsN(C H S ) ] [6], indicating that there is no elec-
7 6 2 2
tronic communication between Ru and Os in 5.
The dimetallic Ru(II)NRe(V) complex {Ru(CO)-
Os(1)ꢀN(1)
Os(1)ꢀS(3)
Os(1)ꢀS(1)
Ru(1)ꢀN(1)
Ru(1)ꢀP(2)
Ru(1)ꢀS(6)
1.680(6)
2.304(3)
2.307(3)
2.068(6)
2.383(2)
2.430(2)
Os(1)ꢀS(4)
Os(1)ꢀS(2)
Ru(1)ꢀC(1)
Ru(1)ꢀP(1)
Ru(1)ꢀS(5)
C(1)ꢀO(1)
2.303(2)
2.306(2)
1.855(8)
2.381(2)
2.427(2)
1.131(8)
(
Et dtc)(PPh ) [NRe(Et dtc) ]}(OTf) (6) was prepared
2
3 2
2
2
similarly from 1 and [ReN(Et dtc) ]. Fig. 5 shows a
2
2
perspective view of the cation {Ru(CO)(Et dtc)-
2
+
(
PPh ) [NRe(Et dtc) ]} ; selected bond lengths and an-
3 2 2 2
N(1)ꢀOs(1)ꢀS(4)
S(4)ꢀOs(1)ꢀS(3)
S(4)ꢀOs(1)ꢀS(2)
N(1)ꢀOs(1)ꢀS(1)
S(3)ꢀOs(1)ꢀS(1)
107.1(2)
85.74(11)
143.71(9)
105.9(2)
145.96(9)
N(1)ꢀOs(1)ꢀS(3) 108.2(2)
N(1)ꢀOs(1)ꢀS(2) 109.1(2)
S(3)ꢀOs(1)ꢀS(2)
S(4)ꢀOs(1)ꢀS(1)
S(2)ꢀOs(1)ꢀS(1)
C(1)ꢀRu(1)ꢀP(1)
C(1)ꢀRu(1)ꢀP(2)
P(1)ꢀRu(1)ꢀP(2) 100.34(7)
N(1)ꢀRu(1)ꢀS(5) 85.43(16)
P(2)ꢀRu(1)ꢀS(5) 165.20(8)
N(1)ꢀRu(1)ꢀS(6)
P(2)ꢀRu(1)ꢀS(6)
gles are listed in Table 6. The geometry around Re is
distorted square pyramidal with Re-to-S4 plane dis-
83.35(11)
placement of 0.71 A
,
. The average RuꢀP, RuꢀS, RuꢀC
84.30(10)
85.69(11)
91.0(2)
and RuꢀN distances in 6 are similar to those for 5. The
ReꢀN and average ReꢀS distances (1.670(3) and 2.381
C(1)ꢀRu(1)ꢀN(1) 169.2(3)
N(1)ꢀRu(1)ꢀP(1)
N(1)ꢀRu(1)ꢀP(2)
C(1)ꢀRu(1)ꢀS(5)
P(1)ꢀRu(1)ꢀS(5)
C(1)ꢀRu(1)ꢀS(6)
P(1)ꢀRu(1)ꢀS(6)
S(5)ꢀRu(1)ꢀS(6)
92.19(16)
95.62(16)
84.1(2)
94.37(8)
87.5(2)
166.13(8)
71.77(8)
93.9(2)
A) are comparable to those for [ReN(Et dtc) ] (1.656(8)
,
2 2
and 2.388 A
RuꢀN bond (2.108(3)
,
, respectively) [22]. The relatively long
and essentially linear
A
,
)
86.86(16)
93.53(8)
RuꢀNꢀRe linkage (170.9(2)°) is indicative of the formu-
lation of ReN“Ru. Accordingly, a high IR CO
stretching frequency (1970 cm ) was observed for 6.
O(1)ꢀC(1)ꢀRu(1) 171.9(7)
−
1
Os(1)ꢀN(1)ꢀRu(1) 166.2(3)
In summary, we have isolated a series of binuclear

H. Zheng et al. / Inorganica Chimica Acta 306 (2000) 184–192
191
+
Fig. 5. Perspective view of the cation [Ru(CO)(Et dtc)(PPh ) {NRe(Et dtc) }] . Phenyl rings of PPh are omitted for clarity. C(92) and C(94) are
2
3 2
2
2
3
hidden by the toluenedithiolate ligands.
Table 6
Acknowledgements
Selected bond lengths (A
PPh ) [NRe(Et dtc) ]}(OTf) (6)
,
) and angles (°) for {Ru(CO)(Et dtc)-
2
(
3
2
2
2
The financial support from The Hong Kong Univer-
sity of Science and Technology and The Hong Kong
Research Grants Council is gratefully acknowledged.
ReꢀS(1)
ReꢀS(3)
ReꢀN(4)
RuꢀS(6)
RuꢀC(1)
O(1)ꢀC(1)
2.378(1)
2.383(1)
1.670(3)
2.418(1)
1.852(4)
1.145(1)
ReꢀS(2)
ReꢀS(4)
RuꢀS(5)
RuꢀP(1)
RuꢀN(4)
2.385(1)
2.378(1)
2.431(1)
2.394(1)
2.108(3)
References
S(1)ꢀReꢀS(2)
S(2)ꢀReꢀS(3)
S(2)ꢀReꢀS(4)
S(1)ꢀReꢀN(4)
S(3)ꢀReꢀN(4)
S(5)ꢀRuꢀS(6)
S(6)ꢀRuꢀP(1)
S(5)ꢀRuꢀN(4)
P(1)ꢀRuꢀN(4)
S(5)ꢀRuꢀC(1)
P(1)ꢀRuꢀC(1)
N(4)ꢀRuꢀC(1)
ReꢀN(4)ꢀRu
73.4(1)
145.4(1)
97.1(1)
106.7(1)
107.3(1)
72.1(1)
87.3(1)
88.0(1)
93.6(1)
89.2(1)
89.4(1)
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