7522 Inorg. Chem. 2009, 48, 7522–7524
DOI: 10.1021/ic901088c
Side-on Coordination of a P-P Bond in Heterobinuclear Tetraphosphorus
Complexes with a [Si(μ,η2:2-P4)Ni] Core and Nickel(I) Centers
Yun Xiong,† Shenglai Yao,† Eckhard Bill,‡ and Matthias Driess*,†
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†Institut fur Chemie, Metallorganik und Anorganische Materialien, Technische Universitat Berlin,
Strasse des 17 Juni 135, Sekr. C2, D-10623 Berlin, Germany, and ‡Max-Planck-Institut fur Bioanorganische
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Chemie, Stiftsstrasse 34-36, 45470 Mulheim/Ruhr, Germany
Received June 5, 2009
The synthesis and characterization of the first heterobinuclear
tetraphosphorus complexes 3a and 3b with a [Si(μ,η2:2-P4)-
Ni] core are reported. The latter result from conversion of the
silylene-activated P4 ligand LSiP4 (1; L = CH[(CdCH2)CMe][N-
(2,6-iPr2C6H3)]2) with the β-diketiminatonickel(I) complexes
[(L0Ni)2 toluene] (L0 = CH[CMeN(2,6-iPr2C6H3)]2) and [(L00Ni)2
toluene] (L00 = CH[CMeN(2,6-Et2C6H3)]2), respectively. Unexpect-
edly, the complexes 3a and 3b feature a [Si(μ,η2:2-P4)Ni] core with
nickel(I) centers as shown by X-ray diffraction analysis, electron
paramagnetic resonance, and magnetic measurements. The
latter prove that the products are paramagnetic both in the solid
state and in solution because of the presence of tetrahedral
nickel(I) sites.
In fact, numerous transition-metal complexes bearing a
tetraphosphorus ligand have been reported since the isolation
of the first transition-metal P4 complex [(PPh3)2ClRh(η2-
P4)].2,3 Meanwhile, the direct activation of white phosphorus
by applying low-valent main-group elements has also
achieved intriguing progress. For instance, reactions of P4
with alkaline organometallic reagents and low-valent group
13 compounds lead to P4-activated species.4a,b Recently, the
activation of P4 was even achieved by using N-heterocyclic
carbenes (NHCs) and carbene-like compounds.4c-f
Remarkably, the zwitterionic N-heterocyclic silylene LSi:
(L = CH[(CdCH2)CMe][N(2,6-iPr2C6H3)]2),5a a heavier
NHC homologue, is also capable of P4 activation to give
the cagelike complex [LSiP4] (1; Scheme 1).5b Interestingly,
one of the P-P bonds in 1 can be further activated by
insertion of a second silylene molecule LSi: to give
[(LSi)2P4] (2).5b The facile P-P bond activation in 1
prompted us to examine whether tricyclic 1 can also react
with low-valent transition-metal centers to give the corre-
sponding heterobinuclear tetraphosphorus complexes
[(LSi)(L0M)P4]. Thus, we probed the reaction of 1 with
3
3
Cyclic silicon-phosphorus species (silaphosphanes) are
electron-rich chelate ligands for transition metals, showing
a versatile coordination chemistry and even finding applica-
tions in metal-mediated catalytic processes.1 Thus, develop-
ing effective routes for the synthesis of versatile
silaphosphane ligands is particularly desirable. The direct
use of white phosphorus as a phosphorus source for the
synthesis of such value-added compounds (phosphorus li-
gands, organophosphanes in organic synthesis, etc.) is an
additional interesting task in contemporary phosphorus
chemistry. The latter process requires facile P4 activation,
which can be achieved by mediation of the transition metals.
the β-diketiminatonickel(I) complex [(L0Ni)2 toluene] (L0=
3
CH[CMeN(2,6-iPr2C6H3)]2),6 which has been success-
fully employed for the activation of dioxygen, octasulfur,
elemental selenium, and tellurium.7 Herein, we report on
the formation of the unusual heterobinuclear complexes
(4) (a) Fox, A. R.; Wright, R. J.; Rivard, E.; Power, P. P. Angew. Chem.,
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*To whom correspondence should be addressed. E-mail: matthias.driess@
tu-berlin.de.
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::
Fritz, G.; Biastoch, R.; Honle, W.; von Schnering, H. G. Z. Anorg. Allg. Chem.
1986, 535, 86. (c) Driess, M.; Faulhaber, M.; Pritzkow, H. Angew. Chem., Int.
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ꢀ
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Published on Web 07/10/2009
2009 American Chemical Society