C. Femoni, M. C. Iapalucci, G. Longoni, S. Zacchini
FULL PAPER
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EXYZ and EADP in SHELXL) were used during refinement for
these positions, and a free variable was assigned to each position.
The overall composition of the cluster was constrained to be in the
ratio Rh:Ni = 2:10 on the basis of ESI-MS analyses. The con-
strained free variable refined as follows: 0.58167 Rh(1), 0.41818
Rh(2) [Ni occupancy factors are the complement at one of each
free variable]. Similar U restraints were applied to the C (s.u. 0.01)
and O (s.u. 0.005) atoms. Restraints to bond lengths were applied
as follow: 1.44 Å (s.u. 0.01) for C–N and 1.53 Å (s.u. 0.01) for C–
C in [NBu4]+.
[5]
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[8]
[NEt4]3[Ni9Rh3C(CO)20]: The unit cell contains four cluster anions
and twelve [NEt4]+ cations (all on general positions). The positions
occupied by M(1), M(2), M(3) and M(4) are disordered Rh and
Ni. Dummy atom constrains (instructions EXYZ and EADP in
SHELXL) were used during refinement for these positions, and a
free variable was assigned to each position. The overall composi-
tion of the cluster was constrained to be in the ratio Rh/Ni = 3:9
on the basis of analytical data and ESI-MS results. The constrained
free variable refined as follows: 0.93509 Rh(1), 0.85178 Rh(2),
0.62743 Rh(3), 0.58511 Rh(4) [Ni occupancy factors are the com-
plement at one of each free variable]. Similar U restraints (s.u.
0.001) were applied to the C and O atoms. Restraints to bond
lengths were applied as follow: 1.47 Å (s.u. 0.01) for C–N and
1.53 Å (s.u. 0.01) for C–C in [NEt4]+. Similar geometries were im-
posed to the three independent [NEt4]+ cations (instruction SAME
in SHELXL).
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[NEt4]4[Ni6Rh8(C2)2(CO)24]·4CH3CN: The unit cell contains eight
cluster anions (only Rh(1), Rh(2), Ni(3), Ni(4), C(1) and six CO
ligands are independent; all other atoms are generated by sym-
metry), 32 [NEt4]+ cations (two halves are independent; all other
atoms are generated by symmetry) and 32 CH3CN molecules (on
general positions). One of the two independent [NEt4]+ cations is
disordered over two positions. Therefore, its atomic positions were
split and refined using one occupancy parameter per disordered
group. Similar U restraints were applied to the C (s.u. 0.001) and
O atoms. Restraints to bond lengths were applied as follows: 1.47 Å
(s.u. 0.01) for C–N and 1.53 Å (s.u. 0.01) for C–C in [NEt4]+;
1.14 Å (s.u. 0.01) for C–N and 1.41 Å (s.u. 0.01) for C–C in
CH3CN.
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[19]
CCDC-715236(for[NBu4]2[Ni10Rh2C(CO)20]),-715235(for[NEt4]3-
[Ni9Rh3C(CO)20]), -715234 (for [NEt4]4[Ni6Rh8(C2)2(CO)24]·
4CH3CN) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[20]
Acknowledgments
A grant of the University of Bologna (CLUSTERCAT) and the
Ministero dell’Università e della Ricerca (MIUR) (PRIN2006) is
gratefully acknowledged.
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