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Novel High-Nuclearity HgCoRu and HgCoFe Sandwich Complexes. Synthesis and Structure of [Hg{RuCo3(-CO)3(CO)9}2]

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[H~?(P~,(,u,-CO)?(PP~IP~~)~J,]
1
[Ag{Pt U.-CO)~(
PIPr3)&1(C F3S03) 2
Complex 2 is obtained in 65% yield as air-stable, darkred prismatic crystals1'I on addition of ca. 1.2 equivalents
of AgCF3S03 to a CH,CI, solution of [Pt3(C0)3(PiPr3)3].
The structure of 2[81 consists of discrete cations and
CF,SO; anions. The cations (Fig. 1) consist of two Pt3
fragments joined by a Ag' ion placed between them on a
crystallographic inversion center. Therefore, the two Pt3
fragments have a staggered configuration. The structure of
the cation is distorted antiprismatic, since two of the Ag-Pt
distances to each triangle (2.828(2) A) are shorter than the
third (2.853(2) A). This type of distortion is observed also
in the Hg,Pt6 cluster 1.l6' The Pt-Pt distances within each
triangular unit are not equivalent, two of them being
longer than those found in the parent Pt, cluster141and in
l.@IThe C O ligands symmetrically bridge the platinum
atoms and are slightly bent towards the silver ion, while
the phosphane ligands bend away from the Pt3 plane. The
mean deviations of the oxyge! and phosphorus atoms
from this plane are 0.8 and 0.9 A, respectively.
[2] a) R. Uson, J. Fornies, M. Tomis, F. A. Cotton, L. R. Falvello, J . Am.
Chem. Soc. 106 (1984) 2482: b) C . E. Briant, R. G. Smith, D. M. P. Mingos. J . Chem. Sac. Chem. Commun. 1984. 586: c) M. Fajardo. M. P. GOmez-Sal, H. D. Holden, B. F. G. Johnson, J. Lewis, R. C. S. McQueen. P.
R. Raithby, J . Organomer. Chem. 267 (1984) C25.
[3] C. E. Briant, R. W. M. Wardle, D. M. P. Mingos, J . Organomet. Chem.
267 (1984) C49.
[4] A. Albinati, lnorg. Chim. Acta 22 (1977) L31.
[5] F. R. Hartley in G. Wilkinson, F. G. A. Stone, E. W. Abel (Eds.): Comprehensive Organome~allicChemirtry, Vol. 6, Pergamon, Oxford 1982, p.
471.
[6] A. Albinati, A. Moor, P. S. Pregosin, L. M. Venanzi, J. Am. Chem. Soc.
104 (1982) 7672.
[7] Satisfactory C, H, Ag, and Pt elemental analyses as well as Ag/P and
Ag/S ratios (determined by X-ray fluorescence) were obtained.
[S] 2 : monoclinic, P2,/c, a=13.277(4), b=25.413(5), c = 12.7120) A,
p=81.27(4)", V=4239.5 A', Z = 2 . Philips PW I100 diffractometer,
MoKn. 20<37.0", 8 / 2 0 scan (0.04" s-I), constant scan-width of 1.20".
2527 observed reflections ( f a 3 o ( o ) . Patterson and Fourier methods.
anisotropic temperature factors for Ag, Pt, and P, isotropic factors for
the other atoms. The CF,SO; anions are strongly disordered over many
positions and their contributions were not taken into account at this
stage of the refinement, which gives R=0.078. However, this does not
affect the main features of the cation.
[9] I9F-NMR (84.66 MHz, CFCI? ext., [DJacetone): S= -79.25
(AgCF3SO3: S= -78.8). The NMR spectra of 2 are similar to those
found for [R,(CO),Ll] [A. Moor, P. S. Pregosin, L. M. Venanzi. Inory.
Chim. Acta 48 (1981) 1531 but show the additional splittings due to the
and , W A g isotopes: "P['HJ-NMR (101.25 MHz, H 7 P 0 4 ext.,
[D,]acetone,
ca. 300 K): 6=61.
'J(RP)=5100, 'J(PtP)=316,
'J(""AgP)=36, LJ('n9AgP)=42,'J(PP)=22.5 Hz; "'R('HJ-NMR (53 53
MHz, K2PtCI, ext., [DJacetone): S= -4776,
'J(PtPt)=2136,
'J( 'I)' '"'AgPt)= 190 Hz (br.).
[lo] a) A. Moor, P. S. Pregosin, L. M. Venanzi, A. J. Welch, Inorg. Chim. Acra
85 (1984) 103, and references cited therein; b) M. Camalli. F. Caruso, S.
Chaloupka, P. N. Kapoor, P. S. Pregosin, L. M. Venanzi. Hrlc. Chim.
Acta 67 (1984) 1603, and references cited therein.
[ I l l In nujol: v = 1855 (w). 1799 (vs), 1762 (m) cm - I . Bands due to CF,SO,
(in KBr) are observed at v = 1270 (s), 1220 (m), I145 (m), and 1030 (m)
cm-'.
I121 L. M. Venanzi, K.-H. Dahmen, unpublished results.
Novel High-Nuclearity HgCoRu and HgCoFe
Sandwich Complexes. Synthesis and Structure
of IHg(RuCo,(~-CO),(CO)~}~l**
Pi
By Pierre Braunstein, * Jacky Rosi, Antonio Tiripicchio,
and Marisa Tiripicchio Camellini
.i
P3
Fig. I . ORTEP diagram of the structure of the cation of 2 in the crystal [8].
Selected bond lengths
and angles ["I: Ag-Ptl 2.853(2), Ag-Pt2 2.825(2),
Ag-Pt3 2.831(2), Ptl-Pt2 2.668(2), Ptl-Pt3 2.657(2), Pt2-Pt3 2.672(2), average
Pt-P 2.28( I), average R - C 2.00(8); Ptl-Pt2-Pt3 59.68(5), PtI-Pt3-Pt2 60.08(5),
Pt2-Pt-Pt3 60.24(5), Ptl-Ag-Pt2 56.05(3), Ptl-Ag-Pt3 55.74(3), Pt2-Ag-Pt3
56.38(3).
[A]
The "P- and '"F't-NMR data are consistent with this
structure if one assumes rapid rotation of the Pt triangles
on the N M R time scale. The values of the chemical shift
and coupling constants['] fall within the expected
ranges.""' The I R spectrum shows three bands in the carbony1 region." 'I
Sandwich complexes of type 2 can be obtained with several phosphanes (e.g., PPhiPr2), and clusters of the type
[Pt3(CO)3Lz]react also with other metal ions (e.g., C u +
and Cd'+), giving products that are analogous to 2.1'21
Thus, there appears to be an extensive coordination chemistry based on Pt,-cluster units.
Received: April 29, 1985;
revised: June 7, 1985 [Z 1281 IE]
German version: Angew. Chem. 97 (1985) 760
[ I ] D G Evans, D. M. P. Mingos, J . Organomel. Chem. 232 (1982) 171, and
references cited therein.
Angen. Chem. Int. Ed. Engl. 24 (1985) No. 9
The isoelectronic character of Au' and Hg" accounts for
the structural analogy found between heteronuclear metalmetal bonded complexes of these ions."] A particularly interesting and rapidly expanding class of mixed-metal clusters is that in which the [AuPR3]@ion, isolobal with Ha,
caps the triangular face of a transition metal cluster.121
The
first examples of a similar bonding mode for the isolobal
[HgX]@ion have recently been reported for X = BrI3' and
X = CO(CO),.[~~
The divalent Hg2@ion has now been found
to react with the anionic clusters [MCO,(CO),~]'( M = Fe,
Ru) with formation of the novel sandwich complexes I
and 2. In particular, the nonanuclear H ~ ( R U C Ocluster
~)~
is formed in 60% yield as stable black-green crystals1s1
upon addition of 2 equivalents of K[RuCo,(CO),,] to
HgBr2 in CHZCl2.It is noteworthy that 2 is also formed[*] Dr. P. Braunstein, Dr. J. Rose
Laboratoire de Chimie d e Coordination, UA 416 CNRS,
Universite Louis Pasteur
4 rue Blaise Pascal, F-67070 Strasbourg Cedex (France)
Prof. A. Tiripicchio, Prof. M. Tiripicchio Camellini
Istituto di Chimica Generale ed Inorganica, Universiti di Parma,
Centro di Studio per la Strutturistica Diffrattometrica del CNR,
1-43 100 Parma (Italy)
[**I Financial support from C N R S and from NATO (Grant 257/83 to P. B.
and A. T . ) is acknowledged.
0 VCH Verlagsgesellschafr mbH, 0-6940 Weinheim. 1985
0570-0833/85/0909-0767 $ 02.50/0
767
along with HgBr,-by
ligand disproportionation of
B ~ H ~ [ R U C ~ , ( C O(CH2CII,
),~]
7 d, 5°C); 2 precipitates directly in the form of crystals that are suitable for X-ray
structure analysis.
troscopic data presently available"'] and by analogy with
the isoelectronic RuCoHg cluster 4.I4l
[HE{MCO,(~-CO),(CO),}~]
1 , M=Fe; 2, M = R u
CAS Registry numbers:
1, 97878-85-8: 2, 97878-86-9; 3, 97878-88-1 ; K[FeCo?(CO),?],90636-09-2:
[(B)Co4(CO),] (B =qh-toluene, 32698-87-6; Et4N[FeCo,(CO),Z],53509-36-7:
K[RUCO,(CO)~~],97878-89-2; BrHg[RuCo3(CO),-]. 97878-90-5; nBu,N[Au12], 50481-03-3; Fe, 7439-89-6: Hg, 7439-97-6; Ru, 7440-18-8; Co,
7440-48-4.
The structure["] of the Hg(RuCo,), cluster 2 consists of
discrete molecules having an imposed C, symmetry, in
which two RuCo, tetrahedral units are joined by a Hg'@
ion placed sandwiched between the Coj planes, at
2.382( 1) A from each plane. Alternatively, this structure
can be viewed as consisting of two trigonal bipyramidal
metal cores HgCo3Ru sharing a common vertex. Since
Hg" is on a crystallographic inversion center, the RuCo,
units are staggered and HgZ@is located in a strongly distorted octahedral cavity. The Co-Hg distances range from
2.777(2) to 2.816(2) A. The other metal-metal distances and
the disposition of the carbonyl ligands are similar to those
found in related RuCo, clusters in which the Co, face is
capped by [CuPPh3]@,[AuPPhj]@"l or [H~CO(CO),]@.[~I
The structure of 2 can also be compared with that of bimetallic Hg(Pt3), clusters.'']
Fig. I . C r ) A atructure of 2. Selected bond distances [A] and angles ["I: HgCo(l) 2.816(2), Hg-Co(2) 2.79 l(3), Hg-Co(3) 2.777(2), Ru-Co( I)2.687(3), RuCo(2) 2.68 1(3), Ru-Co(3) 2.689(4), Co(l)-Co(2) 2.522(2), Co(l)-Co(3)
2.547(2), C0(2)-Co(3) 2.520(2), Co( I)-Hg-Co(2) 53.5( I). Co(l)-Hg-C0(3)
54.2( I), Co(2)-Hg-C0(3) 53.8( I), Co( I)-Ru-Co(Z) 56.0(1), Co( l)-Ru-C0(3)
56.6( I), C O ( ~ ) - R U - C O (56.0(1
~ ) j, C O ( ~ ) - C l)-C0(3)
O(
5Y.6( I), CO(l)-C0(3)Co(2) 59.7( I j, Co(l)-Co(Zj-C0(3) 60.7.
Preliminary reactivity studies indicate that heating
Hg( FeCo,), in toluene leads to metal-metal bond cleavage
with formation of, inter alia, metallic Hg and [(q6-tol~ e n e ) C o ~ ( C O ) ~ ]Interestingly,
.[~l
Et4NCI reacts with 1 in
CHzClz with
extrusion
of
Hg2@, affording
E ~ , N [ F ~ C O , ( C O ) ~and
~ ] "HgCI2.
~~
This opens the way to a
number of double-exchange reactions.
~ B U , N [ F ~ C O , ( ~ - C O ) ~ ( C O ) , { ~ , - A U C O3( C O ) ~ J J
[ R u C O ~ ( ~ - C O ) ~ ( C O ) ~ ( ~ ~ - H S4C O ( C O ) , ~ ~
Q VCH Verlagsgesellsrhaft mbH. 0-6940 Weinheim. 1985
-
P. Braunstein, U. Schubert. M. Burgard. Inorg. Chem. 23 (1984) 4057,
and references cited therein.
P. Braunstein, J. Rose, Gold Bull. 18 (1985) 17.
E. G. Mednikov, V. V. Bashilov, V. 1. Sokolov, Yu. L. Slovokhotov. Yu.
T. Struchkov, Polyhedron 2 (1983) 141.
P. Braunstein, J. Rose, A. Tiripicchio, M. Tiripicchio Camellini, J .
Chem. SOC.Chem. Commun. 1984, 39 1.
Correct elemental analysis. 1: IR (KBrj: r'=2071 (s), 2025 (vs), 1980
(sh), 1920 (w). 1870 (s) c m - ' . U V (CHzCI,): A,,,.,,=330, 616 nm: 2 : IR
(KBr): v=2083 (s), 2033 (YS), 1972 (m), 1912 (w), 1879 (s) em..'. UV
(CH,CI,): A,>
,,,, =326, 365, 548 nm.
Philips PWI 100 diffractometer; C2/c, Z = 4 , a = 14.812(8), b=9.266(6),
c=26.397( 12) A,8=94.75(2)', 3 5 N 5 2 8 ° , 3873 independent reflections,
2574 with 1 2 3 ~ ( 1 )MaKqI
,
radiation, R=0.050, R , =0.068. Further details of the crystal structure investigation are available on request from
the Fachinformationsrentrum Energie Physik Mathematik, D-75 14 Eggenstein-Leopoldshafen 2, on quoting the depository number CSD
5 1 490, the names of the authors. and the full citation of the journal.
P. Braunstein, J. Rose, A. Dedieu, Y. Dusausoy, J. P. Mangeot, A. Tiripicchio, M. Tiripicchio Camellini, J . Chem. Soc. Dalron Trans., in press;
P. Braunstein, J. Rose, Y. Dusausoy, J. P. Mangeot, C. R. Acad. Sci. Ser.
11 294 (1982) 967.
Y. Yamamoto, H. Yamazaki, T. Sakurai, J . Am. Chem. Sac. 104 (1982)
2329: A. Albinati, A. Moor, P. S. Pregosin, L. M. Venanzi, ibrd. 104
(1982) 7672.
G. Bor, G. Sbrignadello, F. Marcati, J . Organomel. Chem. 46 (1972) 357.
P. Chini, L. Colli, M. Peraldo. Gazz. Chrm. l i d . 90 (1960) 1005.
P. Braunstein, R. J . H. Clark. J . Chem. Soc. Dulfon Truns. 1973. 1845.
IR (Nujol): v = 2067 (m). 2010 (va), 1984 (sj, 1973 (s), 1967 (sh), 1925 (m),
1905 (s), 1855(m), 1813(m), 1 7 9 0 ( a ) c m ~I ; UV(CHZCI,)L,,.,,,=505,643
nm.
Reductive Carbonylation of o-Nitrophenol with a
Fe-Pd Cluster-Derived Heterogeneous Catalyst;
CO Migration in IFePdPt(C0)4(PhzPCHzPPh2)zj**
By Pierre Braunstein, * Jacques Kervennal, and
Jean-Luc Richert
Mixed-metal cluster-derived (MMCD) heterogeneous
bimetallic catalysts are of great interest at present because
of their improved catalytic properties over those of conventionally prepared catalysts.11~21
We have recently reported the selective carbonylation of nitrobenzene to phenyl isocyanate,'" using a catalyst obtained from
[Pd2M02(~-C5Hs)2(CO)6(PPh3)2].~31
We have subsequently
become interested in Fe-Pd catalysts for the carbonylation
of o-nitrophenol 1 to benzoxazol-2-one 2, which is a structural element of herbicidesf4' and has a high synthetic potential.
[*] Dr. P. Braunstein, J.-L. Richert
Attempts to synthesize analogous Au-complexes, using
the methods developed above, by reaction of
~ B u , N [ A u I ~ ] [ "with
~
K [ F ~ C O , ( C O ) , ~(THF/H20,
]
O"C,
molar ratio 1 : 2) led to formation of the FeCoAu-cluster 3,
the proposed structure of which is supported by the spec768
Received: May 28, 1985;
supplemented: July 8, 1985 [Z 1315 IE]
German version: Angewj. Chem. 97 (1985) 761
Laboratoire de Chimie de Coordination, UA 416 CNRS
Universite Louis Pasteur
4 rue Blaise Pascal, F-67070 Strasbourg Cedex (France)
Dr. J. Kervennal
Centre de Recherche Rh6ne-Alpes, Atochem
F-9310 Pierre-Binite (France)
[**I
We thank Atochem for a grant to J.-L. R. and CNRS for financial support (ATP Chimie Fine 4384).
0570-0833/85/0909-0768 $ 02.50/0
Angew,. Chem. In!. Ed. Engl. 24 (1988) No. 9
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hgcofe, structure, synthesis, hgcoru, ruco3, high, nuclearity, novem, complexes, sandwich
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