W. Oberhauser et al., STRUCTURAL DIFFERENCES IN NICKEL(II) AND PALLADIUM(II) COMPLEXES CONTAINING CIS-1,2-BIS(DIPHENYLPHOSPHINO)ETHENE OR 1,2-BIS(DIPHENYLPHOSPHINO)ETHANE, Polyhedron, 16(16), 1997, pp. 2827-2835
Monometallic Ni-II and Pd-II complexes of cis-1,2-bis(diphenylphosphin
o)ethene (cis-dppen) or 1,2-bis(diphenylphosphino)ethane (dppe) have b
een prepared and characterized by X-ray diffraction methods, P-31 H-1
NMR spectroscopy, FAB mass spectrometry, elemental analyses and meltin
g points. The X-ray structure of [NiCl2(cis-dppen)] (1) is given for t
he first time. In 1 the mean deviation of the nickel, the phosphorus a
nd the chlorine atoms from a least-squares plane through these atoms i
s only 0.025 Angstrom. The ethene bridge is nearly coplanar with this
plane, which can be explained by a pi-bonding interaction. It is shown
that the small deviation from coplanarity are caused by a crystal pac
king effect. The reaction of Ni(CN)(2) with cis-dppen leads to the nov
el compound [Ni(CN)(2)(cis-dppen)] (2). The removal of chloride in 1 b
y AgBF4 followed by the reaction with 1,10-phenanthroline (phen) leads
to the novel octahedral Ni-II complex [Ni(cis-dppen)(phen)(2)](BF4)(2
) (3). In an analogous manner 2,2'-bipyridine (bipy) produces [Ni(cis-
dppen)(bipy)(2)](BF4)(2) (4). The reaction of trans-1,2-bis(diphenylph
osphino)ethene (trans-dppen) with PdCl2 and subsequent treatment with
LiI leads to the unexpected product [PdI2(dppe)] (5). Compound 5 is al
so fully characterized by an X-ray structure analysis for the first ti
me. The palladium, phosphorus and iodine atoms show a mean deviation o
f only 0.017 Angstrom from a least-squares plane through these atoms.
However, the PdP2C2 chelate ring has a twist conformation, where one c
arbon atom of the aliphatic chain of dppe lies -0.420 Angstrom to one
side, and the second carbon atom 0.318 Angstrom to the other side of t
he coordination plane. In 5 the P-Pd-P chelate angle of 85.59(5)degree
s is significantly smaller than the corresponding P-Ni-P angle of 87.7
9(4)degrees in 1. Furthermore, the X-ray structure of the recently rep
orted complex [Pd(cis-dppen)(2)](BPh4)(2) (6) is given. The palladium
atom is located on a centre of symmetry leading to the complete planar
ity of the coordination plane due to crystallographic constraints. How
ever, the two carbon atoms of the ethene bridge of cis-dppen lie 0.547
and 0.532 Angstrom, respectively, to one side of the coordination pla
ne. Compound 6 significantly shows the smallest P-M-P chelate angle of
84.78(3)degrees compared with the corresponding values in I and 5. A
comparison of the X-tay structures of 1, 5 and 6 with several known X-
ray structures of Ni-II and Pd-II complexes containing cis-dppen or dp
pe is given. Differences in the chelate angles and coplanar parts of t
hese structures are discussed with respect to the observed reactivitie
s of compounds 1-6. (C) 1997 Elsevier Science Ltd.