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New ruthenium(II) hydrido-carbonyl and carbonyl complexes containing triphenylphosphine
INORG.
NUCL.
CHEM.
LETTERS
N E W RUTHENIUM(II)
Vol.
7,
373-377,
1971.
HYDRID0-CARBONYL
CONTAINING
B.R. Department
pp.
Pergamon Press.
AND CARBONYL
P r i n t e d in Great Britain.
COMPLEXES
TRIPHENYLPHOSPHINE
James and L.D. M a r k h a m
of Chemistry, Vancouver,
University
British
of B r i t i s h
Columbia,
Columbia,
Canada.
(Received 12 N o v e m ~ r 1970}
We w i s h to report hydrido-carbonyl ruthenium(II)
the p r e p a r a t i o n
complex (~), RuCIH(C0) 2(PPh3)2,
cis- and trans-
RuC12(CO) 2(PPh3)2, ~ and Solutions
of a new ruthenium(ll)
carbonyls
and new
of f o r m u l a
~.
of R u C I 2 P 3 ( P = P P h 3 )
in d i m e t h y l a c e t a m i d e
(DMA)
take up H2 r a p i d l y at i atm to a I:i mole ratio and f o r m vlolet-red
solutions
containing
the h y d r i d e RuCIHP2,
presum-
ably solvated:
solvent, S ~
RuCI2P 3
This r e a c t i o n
H2 RuCI2P2(S )
is p r o m o t e d
of the l i b e r a t e d proton, amine
is not r e q u i r e d
the h y d r i d e
solvent
and the usual base
(1 - 3).
Under
carbon m o n o x i d e
(JP-H = 19 cps).
of a l:2:l triplet
On c o n c e n t r a t i n g
at 1 atm,
of gas to give
separated
into two w h i t e 373
at T = 14.53
the solution a w h i t e
on r e p e a t e d r e c r y s t a l l i z a t i o n
[i]
such as t r i e t h y l -
solution w h i c h gives a h i g h field proton reson-
ance s p e c t r u m c o n s i s t i n g
precipitates;
+ H + + CI-
systems by solvation
solution r a p i d l y takes up two moles
a pale y e l l o w
this was
in basic
~ RuCIHP2(S)
solid
from C H 2 C 1 2 / M e 0 H
compounds w h i c h analyse for
RUTHENIUM (II) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
374
and ~, respectively.
(~.
Found: C,62.0; H,4.3; CI,4.8.
Calc: C,63.6; H,4.3; C1.4.9. Calo: C,60.6;
Vol. 7, No. 4
~.
Found: C,60.2; H,4.2; C1,9.1.
H,4.0; CI,9.~).
The air-stable hydride ~ dissolved in CH~CI~ to give a colourless solution which gave a proton n.m.r, spectrum identical to that observed for the carbonylated DMA solution; two phosphines cis to hydrogen are indicated.
Carbonyl stretching
frequencies were found at 20~2 and 1995 cm -l in nujol and at 2033 and 1981 cm -l in benzene; these indicate ci~- carbonyls and based on the configurationZdetermined (4,5) for the corresponding complexes with PEt~ (VC0 2042, 1977 cm -I in nujol; 2033, 1969 cm -l in benzene) and PEt2Ph (VCO 2037, 19~0 cm -I in nujol; 2048, 1975 cm -I in benzene), the hydride is formulated as in ~.
Hydridocarbonyl-tertiary phosphine complexes of this
type offer potential use as hydroformylation or hydrogenation catalysts (6-10).
Very slow gas uptake from a C0/H 2 atmosphere
at mild conditions has been observed by solutions of ~ containing alkene substrates.
These studies are being pursued and
will be reported later.
CO
0~ H
CO P
OC,~---- 7 P
C1
CO OC
~
P
C1
The dicarbonyl, 2, (m.pt 230 °) had carbonyl bands at 2038 and 1983 cm -I, with a shoulder at 1967 cm-I in nujol, and at
Vo[. 7, No. 4
RUTHENIUM (11) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
375
2043 and 1979 cm -l in CHsCIs,
and is thus similarly assigned
the ci~-configuration
Other workers
shown.
isolated by a variety of methods complex (m.pt 257e), for example
(4, ll-13) have
a white cis- RuCI~(C0) sP2
having both CO bands some 20 cm -I higher,
(4), 2064 and 2001 cm -l, and this has been assigned
configuration ~ (4). quite different and we believe
We have also made this complex,
to that prepared from our hydride
which is
solutions,
it must have configuration ~ or ~.
Wilkinson
and Stephenson
tr~ns- dicarbonyl ,
(4) prepared a pale yellow
which undoubtedly
with VC0 at 2005 cm -I.
Another
(4,5) has configuration
deeper yellow trans-lsomer
with VC0 at 1920 cm -l was detected but could not be obtained pure.
Both the trans isomers were readily converted
tion to the cis compound (VC0 = 2064, 2001 cm-1). the dark yellow trans-isomer
is the sole
CI
product
of carbonyla-
CO
3-7
i
CI
CI
of a suspension
of RuCIsP3
room temperature;
the complex,
uration
, analyses
6
We find that
CI P
tlon (I arm)
in solu-
at 1922 cm -I (nujol mull).
CO
in dimethylformamlde
at
which must have config-
correctly and has a single CO band Recrystallization
from CH~CI~/Me0H without heating;
can be effected
the recrystallized
shows a second band at 1934 cm -z (nujol)
product
but in CH2C1 ~solution
RUTHENIUM (ll) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
376
a single band at 1943 cm -l is observed. CH~C~a
Vol. 7 , No. 4
After several hours in
band starts to appear at 1977 cm-1; this is presumably
due to isomerization to ~. A solution of RuC12P3 in DMA takes up 2 moles of CO to give a dark yellow solution which contains both trans forms,~ and ~, but on concentrating the solution, ~ precipitates
in pure form.
We thank the National Research Council of Canada for support of this research and Johnson Matthey Ltd. for loan of the ruthenium.
References 1.
P.S. Hallman,
B.R. McGarvey and G. Wilkinson,
J. Chem. Soc. (A),
3143 (1968). 2.
B. Hui and B.R. James,
Chem. Comm., 198 (1969).
3.
B. Hui and B.R. James, Proc. 4th Intern. metallic Chem., Bristol,
4.
1969.
Conf. on 0rgano-
Abstract L6.
T.A. Stephenson and G. Wilkinson,
J. Inorg. Nucl. Chem., 28,
945 (1966). 5.
J. Chatt, B.L. Shaw and A.E. Field, J. Chem. Soc., 3466 (1964).
6.
B.R. James, Inorg. Chim. Acta Rev. ~ (1970),
7.
C. O'Connor and G. Wilkinson,
8.
D. Evans, J.A. Osborn and G. Wilkinson,
in press.
J. Chem. Soc. (A), 2665 (1968). J. Chem. Soc. (A),
3133 (1968). 9.
G. Pregaglia,
A. Andreetta,
G. Ferrari and R. Ugo, Chem.
Comm., 590 (1969). 10.
M. Hidai, T. Kuse, T. Hikita, Y. Uchida and A. Misono, Tetrahedron Letters,
1715 (1970).
Vol. 7, No. 4
ll.
RUTHENIUM (II) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
377
J.P. Collman and W.R. Roper, J. Amer. Chem. Soc., 8_~, 4008 (1965).
12.
M.I. Bruce and F.G.A. Stone, J. Chem. Soc. (A), 1238 (1967).
13.
J.D. Cotton, M.I. Bruce and F.G.A. Stone, J. Chem. Soc. (A), 2162 (1968).
NUCL.
CHEM.
LETTERS
N E W RUTHENIUM(II)
Vol.
7,
373-377,
1971.
HYDRID0-CARBONYL
CONTAINING
B.R. Department
pp.
Pergamon Press.
AND CARBONYL
P r i n t e d in Great Britain.
COMPLEXES
TRIPHENYLPHOSPHINE
James and L.D. M a r k h a m
of Chemistry, Vancouver,
University
British
of B r i t i s h
Columbia,
Columbia,
Canada.
(Received 12 N o v e m ~ r 1970}
We w i s h to report hydrido-carbonyl ruthenium(II)
the p r e p a r a t i o n
complex (~), RuCIH(C0) 2(PPh3)2,
cis- and trans-
RuC12(CO) 2(PPh3)2, ~ and Solutions
of a new ruthenium(ll)
carbonyls
and new
of f o r m u l a
~.
of R u C I 2 P 3 ( P = P P h 3 )
in d i m e t h y l a c e t a m i d e
(DMA)
take up H2 r a p i d l y at i atm to a I:i mole ratio and f o r m vlolet-red
solutions
containing
the h y d r i d e RuCIHP2,
presum-
ably solvated:
solvent, S ~
RuCI2P 3
This r e a c t i o n
H2 RuCI2P2(S )
is p r o m o t e d
of the l i b e r a t e d proton, amine
is not r e q u i r e d
the h y d r i d e
solvent
and the usual base
(1 - 3).
Under
carbon m o n o x i d e
(JP-H = 19 cps).
of a l:2:l triplet
On c o n c e n t r a t i n g
at 1 atm,
of gas to give
separated
into two w h i t e 373
at T = 14.53
the solution a w h i t e
on r e p e a t e d r e c r y s t a l l i z a t i o n
[i]
such as t r i e t h y l -
solution w h i c h gives a h i g h field proton reson-
ance s p e c t r u m c o n s i s t i n g
precipitates;
+ H + + CI-
systems by solvation
solution r a p i d l y takes up two moles
a pale y e l l o w
this was
in basic
~ RuCIHP2(S)
solid
from C H 2 C 1 2 / M e 0 H
compounds w h i c h analyse for
RUTHENIUM (II) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
374
and ~, respectively.
(~.
Found: C,62.0; H,4.3; CI,4.8.
Calc: C,63.6; H,4.3; C1.4.9. Calo: C,60.6;
Vol. 7, No. 4
~.
Found: C,60.2; H,4.2; C1,9.1.
H,4.0; CI,9.~).
The air-stable hydride ~ dissolved in CH~CI~ to give a colourless solution which gave a proton n.m.r, spectrum identical to that observed for the carbonylated DMA solution; two phosphines cis to hydrogen are indicated.
Carbonyl stretching
frequencies were found at 20~2 and 1995 cm -l in nujol and at 2033 and 1981 cm -l in benzene; these indicate ci~- carbonyls and based on the configurationZdetermined (4,5) for the corresponding complexes with PEt~ (VC0 2042, 1977 cm -I in nujol; 2033, 1969 cm -l in benzene) and PEt2Ph (VCO 2037, 19~0 cm -I in nujol; 2048, 1975 cm -I in benzene), the hydride is formulated as in ~.
Hydridocarbonyl-tertiary phosphine complexes of this
type offer potential use as hydroformylation or hydrogenation catalysts (6-10).
Very slow gas uptake from a C0/H 2 atmosphere
at mild conditions has been observed by solutions of ~ containing alkene substrates.
These studies are being pursued and
will be reported later.
CO
0~ H
CO P
OC,~---- 7 P
C1
CO OC
~
P
C1
The dicarbonyl, 2, (m.pt 230 °) had carbonyl bands at 2038 and 1983 cm -I, with a shoulder at 1967 cm-I in nujol, and at
Vo[. 7, No. 4
RUTHENIUM (11) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
375
2043 and 1979 cm -l in CHsCIs,
and is thus similarly assigned
the ci~-configuration
Other workers
shown.
isolated by a variety of methods complex (m.pt 257e), for example
(4, ll-13) have
a white cis- RuCI~(C0) sP2
having both CO bands some 20 cm -I higher,
(4), 2064 and 2001 cm -l, and this has been assigned
configuration ~ (4). quite different and we believe
We have also made this complex,
to that prepared from our hydride
which is
solutions,
it must have configuration ~ or ~.
Wilkinson
and Stephenson
tr~ns- dicarbonyl ,
(4) prepared a pale yellow
which undoubtedly
with VC0 at 2005 cm -I.
Another
(4,5) has configuration
deeper yellow trans-lsomer
with VC0 at 1920 cm -l was detected but could not be obtained pure.
Both the trans isomers were readily converted
tion to the cis compound (VC0 = 2064, 2001 cm-1). the dark yellow trans-isomer
is the sole
CI
product
of carbonyla-
CO
3-7
i
CI
CI
of a suspension
of RuCIsP3
room temperature;
the complex,
uration
, analyses
6
We find that
CI P
tlon (I arm)
in solu-
at 1922 cm -I (nujol mull).
CO
in dimethylformamlde
at
which must have config-
correctly and has a single CO band Recrystallization
from CH~CI~/Me0H without heating;
can be effected
the recrystallized
shows a second band at 1934 cm -z (nujol)
product
but in CH2C1 ~solution
RUTHENIUM (ll) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
376
a single band at 1943 cm -l is observed. CH~C~a
Vol. 7 , No. 4
After several hours in
band starts to appear at 1977 cm-1; this is presumably
due to isomerization to ~. A solution of RuC12P3 in DMA takes up 2 moles of CO to give a dark yellow solution which contains both trans forms,~ and ~, but on concentrating the solution, ~ precipitates
in pure form.
We thank the National Research Council of Canada for support of this research and Johnson Matthey Ltd. for loan of the ruthenium.
References 1.
P.S. Hallman,
B.R. McGarvey and G. Wilkinson,
J. Chem. Soc. (A),
3143 (1968). 2.
B. Hui and B.R. James,
Chem. Comm., 198 (1969).
3.
B. Hui and B.R. James, Proc. 4th Intern. metallic Chem., Bristol,
4.
1969.
Conf. on 0rgano-
Abstract L6.
T.A. Stephenson and G. Wilkinson,
J. Inorg. Nucl. Chem., 28,
945 (1966). 5.
J. Chatt, B.L. Shaw and A.E. Field, J. Chem. Soc., 3466 (1964).
6.
B.R. James, Inorg. Chim. Acta Rev. ~ (1970),
7.
C. O'Connor and G. Wilkinson,
8.
D. Evans, J.A. Osborn and G. Wilkinson,
in press.
J. Chem. Soc. (A), 2665 (1968). J. Chem. Soc. (A),
3133 (1968). 9.
G. Pregaglia,
A. Andreetta,
G. Ferrari and R. Ugo, Chem.
Comm., 590 (1969). 10.
M. Hidai, T. Kuse, T. Hikita, Y. Uchida and A. Misono, Tetrahedron Letters,
1715 (1970).
Vol. 7, No. 4
ll.
RUTHENIUM (II) HYDRIDO-CARBONYL AND CARBONYL COMPLEXES
377
J.P. Collman and W.R. Roper, J. Amer. Chem. Soc., 8_~, 4008 (1965).
12.
M.I. Bruce and F.G.A. Stone, J. Chem. Soc. (A), 1238 (1967).
13.
J.D. Cotton, M.I. Bruce and F.G.A. Stone, J. Chem. Soc. (A), 2162 (1968).