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2258 J. Chem. SOC.(A), 1970

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The Preparation, Reactions, and Infrared Spectra of Some Derivatives of

Bis(tricarbony1nitrosy1iron)mercury
By M. Casey and A. R. Manning,* Department of Chemistry, University College, Belfield, Dublin 4
Complexes of the type [Hg(Fe(CO),(NO)L),] [L = R,P, (RO),P, R,As, and R,Sb; R = alkyl or aryl] have been
prepared. They react with mercury(i1) halides to give [XHgFe(CO),(NO) L] derivatives, some of which have been
isolated (L = CO and PhEt,As; X = Br and I ) . The i.r. spectra of both series of compounds indicate that they
possess linear L-Fe-Hg-X systems [X = CI, Br, I, and Fe(CO),(NO) L] with trigonal bipyramidal co-ordination
about the iron atoms. The parent comDound, [Hg{Fe(CO),NO),], dissociates completely in dimethyl sulph-
oxide solution to give the [Fe(CO),NO]- ion. The substituted derivatives do not ionize.

BOTHbis(tetracarbonylcobalt)mercury, [Hg(CO(CO),},]
and the isoelectronic compound [Hg(Fe(CO),NO),]
,:
undergo carbonyl substitution reactions with tertiary
phosphine, arsine, and stibine ligands, L, to give deriva-
tives-of the type [H~{CO(CO),L),],~-~ and [Hg{Fe(CO),-
(NO)L)91
. . .--*697
Spectral 8-10 and X-ray diffraction studies l1*l2 have
shown that [Hg(Co(CO),),] has D,, symmetry, and that
both of its axial carbonyl ligands are replaced in the
substituted compounds [Hg(Co(CO),L),] .13-15 The i.r.
spectrum of [Hg(Fe(CO),NO},] indicates that it is iso-
centrosymmetric structure, but the relative orientations
of the nitrosyl ligands could not be determined.le
I t seemed reasonable to expect that [Hg{Fe(CO),-
(NO)L},] complexes would be isostructural with [Hg{Co-
(CO),PEt,),] ,16 and undergo many similar reactions.
Therefore, we have prepared a number of such com-
pounds, investigated their i.r. spectra in the C-0 and
N-0 stretching regions (1600-2100 cm-l), and compared
the reactions of unsubstituted and substituted compounds
with those undergone by carbonylcobalt-mercury, e.g.
exchange with mercury(I1) halides,,, l8 mercury ex-
179

structural with its cobalt analogue. It does not have a
W. Hieber and U. Teller, 2. anorg. Chem., 1942, 249, 43.
W. Hieber and H. Beutner, 2. anorg. Chem., 1963, 320, 101.
W. Hieber and R. Breu, Chem. Ber., 1957, 90, 1259.
F. Bonati, S. Cenini, and R. Ugo, J . Chem. SOL. ( A ) ,1967,
932.
R. B. King, Inorg. Chem., 1963, 2, 936.
it R. B. King, Inorg. Chem., 1963, 2, 1275.
W. Hieber and W. Klingshirn, Z . nnorg. Chem., 1963, 323,
292.
H. Stammreich, K. Kawai, 0. Sala, and P. Krumholz,
J . Chem. Phys., 1961, 35, 2175.
G. Bor and L. Marko, Spectrochim. Acta, 1960, 16, 1105.
lo K. Noack, Helv. Chim. Acta, 1964, 47, 1555.
l1 G. M. Sheldrick and R. N. F. Simpson, Chem. Comm., 1967,
1015.
l2 G. M. Sheldrick and K. N. F. Simpson, J . Chem. Soc. ( A ) ,
1968, 1005.
l3 A. R. Manning, J . C k m . SOL.( A ) , 1968, 1018.
14 L. M. Bower and M. H. B. Stiddard, J . Organometallic
Chem., 1968, 13, 235.
l5 R. F. Bryan and A. R. Manning, Chem. Comm., 1968, 1316.
TV. Beck and K. Noack, J . Organometallic Chem., 1967, 10,
307.
1 0. Kahn, J. Henrion, and G. Bouquet, Bull. Soc. chim.
'
France, 1967, 3547.
l8 B. J . Aylett and J. M. Campbell, J . Chem. ( A ) , 1969, 1910.
 View Article Online

Inorg. Phys. Theor. 2259

change with zinc and cadmium,lg and ionic dissociation
in polar solvents such as acetonitrile.,')
EXPERIMENTAL
Most chemicals were purchased from commercial sources
e.g. Bun3P, Ph,P, (MeO),P, (EtO),P, (PriO),P, (PhO),P,
Ph3As, and Ph,Sb. The remaining ligands were prepared
complete within 5 min. The solvent was removed at
reduced pressure and the residue was extracted with
benzene, pentane was added to the extract to precipitate
the products, which were then crystallized from benzene-
hexane (yields >60%). Analytical and melting point
data for these compounds are given in Table 2.
TABLE2

-
by standard techniques,21,22whilst the method of Hieber Melting point and analytical data for complexes
and Beutner was used for bis (tricarbonylnitrosyliron) - [XHgFe (CO) (N0)L
mercury .2* 23
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All reactions described here were carried out in deoxy-

Found (%) Required (yo)
genated solvents under nitrogen in the dark a t room L X M.p."$b C H N L F - G - 3
temperature. Solutions of [Hg(Fe(CO),NO),] (cu. 1 g) and co Br dec. 99 7.8 2.8 8.0 3.1
the ligands, L, (mol ratio of 1 : 2) in benzene (cu. 50 ml) were co I 91 7-1 3.0 '7.2 2.8
PhEt2As Br 86-87(d) 22.3 2.4 2.1 22.8 2.4 2.2
stirred for three to forty-four hr. The reactions were PhEtZAs I 84-85(d) 20.7 2.3 1.8 21.2 2.2 2.0
monitored spectroscopically. The ligands Ph2MeP, Et,As, ~ J See
J Table 1.
Ph,MeAs, and Et3Sb were markedly more reactive than the
others.
As the derivatives of Ph3P, Ph3As, and Ph3Sb were The chloromercury analogues of these compounds were
very unstable and were not isolated, 1.r. spectral evidence
insoluble in organic solvents, they were filtered off, and
washed with hot benzene. Other complexes were isolated was obtained for the formation of other [FeL(CO),(NO)HgX]
by removal of the solvent from the filtered reaction mixtures. derivatives by the same route ( L = Ph,P, (MeO),P,
Those of Bun3P and Bun,Sb were separated from other (PriO),P, (PhO),P, Et3As, and Et,Sb; X = Br and I}.
products, [FeL(CO)(NO)J, [FeL,(NO) 2] and trans-[FeL,- However, no attempt was made to isolate them.
(CO),] (L = Bun3P and Bun3Sb), by chromatography, and 1.r. spectra were obtained with Perkin-Elmer 125 and
337 spectrometers ; they were calibrated with deuterium
recrystallized from methanol. In all other instances only
the [Hg{Fe(CO),(NO)L},] compounds were obtained ; these chloride and water v a p o ~ r . The
~ ~ spectra in the 1600-
were recrystallized from benzene or benzene-hexane. 2100 cm-1 region are summarised in Tables 3 and 4.
Reaction yields were ca. 20% for L = Bun3P and Bun3Sb,
30-50% for L = Et3P, (MeO),P, (EtO),P, (PriO),P, and RESULTS AND DISCUSSION
Et,Sb, and > S O % in all other instances. Melting point Although [Hg(Fe(CO),NO),] undergoes carbonyl sub-
and analytical data for [Hg{Fe(CO),(NO)L),] derivatives are stitution in the same way as [Hg(Co(CO),),] to give
given in Table 1. [Hg(Fe(CO),(NO)L),] complexes, the reactions are much
TABLE 1 slower and the yields lower due to side reactions or
Melting point and analytical data for the complexes product decomposition. However, whereas bis(tetra-
F w F e ( C O )2(NO)L}*I
carbonylcoba1t)mercury gives [(Co(CO),P(OMe),},] on
Found (76) (yo)
Required
reaction with trimethyl p h o ~ p h i t ethe
, ~ iron compound
L
*
h1.p. ( " C ) O J '
C H N
*
C H N
yields only direct substitution products with trialkyl
phosphite ligands. No derivatives of [Fe,(C0)6(N0)2]
co 87-88 13.8 4.9 13.3 6.2
were detected.
Et,P 140-141 26.7 4.2 3.9 26.5 4.2 3.9
Bun,P 115-116 38.2 6.4 3.0 37.8 6.1 3.1 The nitrosyliron complexes are dark yellow to orange
Ph,MeP 147(d) 40.6 2.9 3.1 40.5 2.9 3.1 crystalline solids and are much less stable than their
Ph,P dec. 196 48.0 3.0 2.7 47.6 3.0 2-8
(MeO),P 99-l00(d) 16.7 2.6 16.3 2.5 3.7 cobalt analogues. Those of the type [Hg{Fe(CO),-
(EtO),P 103-104 23.2 3-8 3.0 23.3 3.7 3.4 (NO)P(OR,)}J ( R = Me, Et, or Pri) decompose slowly
(PriO),P 127--129(d) 29.7 4.7 2.7 29.5 4.7 3.1
(PhO),P 138 43.3 2-5 43.3 2.7 2.5
even in the solid state a t -20°C under nitrogen. In
Et,As 134--135(d) 23.7 3.7 3.4 23.6 3.7 3.4 solution, all were unstable, especially in the presence of
PhEt2As 71-72 32.2 3.0 3.0 31.8 3.3 3.1 light and decomposed to give [FeL(CO)(NO),] derivatives
Ph,MeAs 131-132(d) 37.2 2-7 36.9 2.7 2.9
Ph,As dec. 170 43.6 2.9 2.5 43.5 2.7 2-5 [L = CO, R3P, (RO),P, R,As and R3Sb]. A similar
Et,Sb dec. 79 21.6 3.5 21.2 3.3 3.1 decomposition has already been noted for [Hg{Fe-
Bun3Sb 61-62 31.3 4.9 2.4 31.3 5.0 2.6
Ph,Sb dec. 175 40.4 2.6 2.2 40.2 2.6 2.4 (CO),NO),] ., The instability was especially marked for
Sealed tubes. (d) = melts with decomposition; dec. [Hg(Fe(CO),(NO)PBu,>,], which accounts partially for
= decomposes without melting. the low yield of this complex. The decomposition could
be followed spectroscopically, and absorption bands due
The complexes [FeL(CO),(NO)HgX] (L = CO and to the products identified. They are not included in
PhEt,As; X = Br and I) were prepared by the addition of Table 3.
a large excess of mercury(I1) halide to a solution of [Hg-
22 D. M. Adams and J. B. Raynor, 'Advanced Practical
(Fe(CO),(NO)L},] (ca. 1 g) in acetone. The reactions were Inorganic Chemistry,' John Wiley and Sons Ltd., London, 1965,
p. 116.
19 J . M.Burlitch, J. Ovganometallic Chem., 1967, 9, 9. 23 R. B. King, ' Organometallic Syntheses,' Academic Press,
20 J. M. Burlitch, J. Amev. Chem. Soc., 1969, 91,4562. London, 1965, p. 165.
2 1 G. J . Burrows and E. E. Turner, J. Chem. Soc., 1920, 117, 24 ' Tables of Wavenumbers for the Calibration of Infrared
1373. Spectrometers,' Butterworths, London, 1961.
 View Article Online

2260 J. Chem. SOC.(A), 1970

TABLE3
The i.r. spectra of the complexes [Hg{Fe(CO),(NO)L},]between 1600 and 2100 cm-l. Peak position (cm-l) and relative
peak heights in parentheses. The solvent is heptane unless stated otherwise
Absorption bands (I

L Ab B" Cc D C E c F C

CO 1769(2.5) 1786(2-7) 1980sh 1986(6.1) 2005(1*7)

20 14 (0-9) 2051( 10) 2072 (0.8)
Et,P 1715(3.6) 1729(3.6) 1915sh 1921(10) 1956(3*8) 1982(2*1)
Bun,P 1714(3*7) 1727(3.5) 1913sh 1918(10) 1954(3*8) 1981(2.1)
Ph,MeP d 1712(4-2) 1726(4.5) 1918(10) 1957(3.6) 1983(2*5)
Ph,P 1715(6.6) 1725(6.1) 1917(10) 1924sh 1963(4*2) 1989(3-2)
(MeO),P 1728( 5-0) 1745(4-6) 1939sh 1943(10) 1975(4*0) 2002(2.2)
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( E t0 )BP 1724(5.1) 1740(4.7) 1935sh 1940(10) 1972 ( 3* 9) 2000(2.4)

( PriO) ,P 17lg(5.2) 1733(4*5) 1928sh 1937(10) 1967 ( 3.8) 1997(2-3)
(PhO)3p 1740(4.8) 1755(5.2) 1945sh 1949(10) 1983(4*0) 2007(2.3) 2024(2.6)f
Et,As 1717(3.1) 1730(3*1) 1913sh 1920(10) 1957(3.2) 1982(2*1)
PhEt,As 1720(3.7) 1733(3-3) 1922(10) 1960(3*3) 1984(2*1)
Ph,MeAs d 1715(4.7) 1727(6.0) 1910sh 1919(10) 1960(3.2) 1984(2.2)
Ph,As e 17 15(6.6) 1726(6*0) 1914(10) 1924sh 1965(4*3) 1990(3-2)
Et,Sb 1719(4.0) 1731(3.9) 1910sh 1918(10) 1954(2.8) 1977(1.9)
Bun,Sb 1718(3.9) 1730(4*0) 1911sh 1918( 10) 1955(3-2) 1977(2*2)
Ph,Sb 1715(6.5) 1725(6*5) 1918( 10) 1925sh 1964(3.5) 1987 (2.9)
(Ish = Shoulder. b Due t o v(N0) vibrations. c Due t o v(C0) vibrations. Carbon disulphide solution. C KBr disc.
f We are unable t o account for this absorption band. It may be due t o isomerism, but i t is not due to decomposition.

The i.r. spectra between 1600 and 2100 cm-l of all com- tensity relationships derived by Beck et aL25 may still
pounds are summarised in Table 3. Their similarity be used. They indicate that the angle between the two
point to similar structures in all cases, whilst the vari- N-0 bonds is less than 90". Despite the well-known
ations in the frequencies of absorption bands due to nonlinearity of some M-N-0 s y ~ t e m s , ~ ~the
3 ~ ' angle
v(NO), A and B, v(C0) vibrations, C-F, with L are as 0
expected on the basis of the x-acceptor properties of L. 0 0 N

TABLE 4
The i.r. spectra of XHgFe(CO),(NO)L complexes between
1600 and 2100 cm-l. Peak positions (cm-l) with rela-
tive peak heights in parentheses. The solvent is
\/
I\
chloroform unless stated otherwise.
L X Absorption bands
co c1 1798(7*4)a 2000(9-3) 2031(4-2) 2083(10)
co Br 1792(7-1) 1998(8-7) 2028(4-2) 2080( 10) I c c
co I b 1794(7-2) 1996(8-8) 2026(3.9) 2077(10) C 0 0
Ph,P I 1746(6-7) 1943(10) 2000(3.'i) 0
(MeO),P I 1757(7*0) 1953(10) 2010(4*2)
( PriO) ,P I 1747(6*9) 1948(10) 2006(4*4) The proposed structure for [Hg{Fe(CO),(NO)L),] complexes
(PhO)s p I 1764(7.3) 1959(10) 2013(4*1)
Et,As I 1738(6-4) 1935(10) 1992(3*8) between the two Fe-N bonds is also probably less than
PhEt,As c1 1743(6.0) 1939(10) 1994(2.9) 90". As it is likely that the Hg-Fe-N angles are close
PhEt,-%s Br QJ 1748(5-7) 1943(10) 1997(2*9)
PhEt,As 1Q d 1746(6*0) 1940(10) 1994(3*2) to 90" (cj. refs. 11, 12, and 15), this could only be the
Et,Sb I 1736(6.6) 1930(10) 1986(3*6) case if the two sets of radial ligands adopt a staggered
Absorption bands due t o v(N0) vibrations, the others are rather than an eclipsed conformation, with an ON*Fe*-
due t o v ( C 0 ) modes. Only these compounds were isolated. Hg*Fe*NOdihedral angle of ca. 60". Such a molecule
c Carbon disulphide solution. d Heptane solution.
would have C, symmetry and be expected to give rise to
It is probable that in these compounds there is a linear four i.r.-active v(C0) vibrations. Three such absorp-
L-Fe*Hg*Fe*L system with one nitrosyl and two carbonyl tion bands are always observed, and in some instances
ligands lying in the equatorial plane about each iron a shoulder may also be detected (Table 3).
atom (Figure). As there is no evidence for structural Although the i.r. spectrum of [Hg(Fe(CO),(NO)},] is
isomerism, the presence of two absorption bands due to the same in heptane, carbon disulphide, xylene, and
v(N0) vibrations eliminates the possibility of centro- chloroform solutions, in donor solvents three new absorp-
symmetric structures. Absorption bands A and B have tion bands are observed a t 1983(2.5), 1881(10), and
comparable peak heights, but their band widths differ; 1651 (4.4) cm-l in dimethyl sulphoxide solution. These
B is the broader. Even though the two nitrosyl ligands bands are due to the [Fe(CO),NO]- ion (cf. ref. 28)
are not co-ordinated to the same metal atom, t h e in- formed in a reversible ionization similar t o that reported
for [Hg(Co(CO),},] and many other compounds con-
s W. Beck, A. Melinkoff, and R. Stahl, Chem. Ber., 1966, 99,
3721. 27 D. J. Hodgson and J. A. Ibers, Inovg. Chena., 1969, 8, 1282,
26 M. A. Bush, G. A. Sim, G. R. Knox, M. Ahmad, and C. G. and references therein.
Robertson, Chem. Comm., 1969, 74. 28 W. Beck, Chem. Bey., 1961, 94, 1214.
 View Article Online

Inorg. Phys. Theor. 2261

taining metal-metal bonds.,O Although dissociation is unstable, but do not disproportionate in heptane solu-
complete in dimethyl sulphoxide solution, it is not ob- tion. Their i.r. spectra (Table 4) show one absorption
served in tetrahydrofuran, and is only partial in pyridine,band due t o v(N0) and two due to v(C0) vibrations.
acetonitrile, and diglyme. Dilution of solutions in The relative intensities of the latter pair indicate an
these last three solvents causes an increase in the degree OC-Fe-CO bond angle of ca. 120°.*25 Thus it is prob-
of dissociation. There is no evidence for a similar able that in these compounds there is trigonal-bi-
ionization of the substituted compounds [Hg{Fe(CO),- pyramidal co-ordination about the iron atom with the
“O)L},I- ligand L and the HgX group occupying the apical co-
Many complexes of mercury(11) undergo ligand- ordination positions.
exchange reactions. For example, [{ Mo (x-C,H,) (CO)3)2- Bis(tetracarbonylcoba1t)mercury undergoes mercury
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Hg] and HgX, (X = C1, Br, or I) give [Mo(x-C,H,)- exchange reactions with metallic cadmium or zinc to
(CO),HgX] ,29 whilst disproportionation is also known. give [Zn(Co(CO),),] or [Cd(Co(CO),),] .19 Similar re-
For example, (MeHg),Fe(CO), decomposes readily to actions have been attempted with [Hg{Fe(CO),NO},],
dimethylmercury and the polymer [{HgFe(CO)4}n] .30 but the only product which could be detected spectro-
Like [H~(CO(CO),),],~~~~J* [Hg{Fe(CO),NO},] reacts scopically in either instance was [Fe(CO),(NO),]. How-
with mercury(11) halides to give the unstable yellow ever, under the same conditions, [Hg{Fe(CO),NO),]
crystalline [XHgFe(CO),NO] (X = Br or I). These alone shows very little decomposition to mononuclear
disproportionate to the parent compounds in n-heptane, species during 24 hr. In the presence of cadmium or
and, to a lesser extent, in carbon disulphide solutions, zinc metal, after this time only [Fe(CO),(NO),] could
but not in chloroform. Spectroscopic evidence also be detected spectroscopically. This suggests that
indicates that similar reactions occur for the substituted [Zn(Fe (CO)3N0}2] or [Cd(Fe (CO)3N0>,I is first formed,
derivatives (Table 4), but we have only isolated [XHgFe- but being unstable, decomposes rapidly.
(CO),(NO)AsEt,Ph] (X = Br or I). They also are
[0/342 Received, March 2nd, 19701
* The coupling of u ( N 0 ) and v ( C0 ) vibrations has been
ignored. However, other work carried out in these laboratories 29 31. J. Mays and J. D. Robb, J . Chem. SOC.( A ) , 1968, 329.
indicate that it is probably negligible. 30 Fr. Heim and H. Pobloth, 2.anorg. Chem., 1941, 248, 84.