Towards heteronuclear triple bonds involving silicon or germanium

Article abstract of DOI:10.1080/10426507.2010.543106

(Graph Presented) The thermal stability of stannylated phosphanosilanes/ germanes has been explored, where chlorostannane elimination should yield multiply bonded systems. Although destannylation occurs, the resulting products are hydrophosphanes and polymeric materials. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426507.2010.543106

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Towards Heteronuclear Triple Bonds
Involving Silicon or Germanium
Rudolf Pietschnig a & Andreas Orthaber a
a Institute of Chemistry, Inorganic Chemistry , Karl Franzens
University Graz , Graz , Austria
Published online: 16 Jun 2011.
To cite this article: Rudolf Pietschnig & Andreas Orthaber (2011) Towards Heteronuclear Triple Bonds
Involving Silicon or Germanium, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:6,
1361-1363, DOI: 10.1080/10426507.2010.543106
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Phosphorus, Sulfur, and Silicon, 186:1361–1363, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.543106
TOWARDS HETERONUCLEAR TRIPLE BONDS INVOLVING
SILICON OR GERMANIUM
Rudolf Pietschnig and Andreas Orthaber
Institute of Chemistry, Inorganic Chemistry, Karl Franzens University Graz,
Graz, Austria
GRAPHICAL ABSTRACT
Abstract The thermal stability of stannylated phosphanosilanes/germanes has been explored,
where chlorostannane elimination should yield multiply bonded systems. Although destanny-
lation occurs, the resulting products are hydrophosphanes and polymeric materials.
Keywords Germanium; multiple bonds; NMR; phosphorus; silicon; tin
INTRODUCTION
Recently, the groups of Wiberg,1 Sekiguchi,2 and Tokitoh3 have demonstrated inde-
pendently that stable compounds containing a silicon–silicon triple bond can be stabilized
by a combination of steric and electronic effects. Other stable triply bonded silicon species
are, however, unknown to date despite several attempts. We ourselves prepared precursors
1a,b, which upon chlorostannane elimination should be prone to generate SiP and GeP mul-
tiply bonded systems.4,5 Moreover we explored the possibility to approach -Si≡C- units via
conjugate addition to suitably functionalized alkynylsilanes,6,7 which in the course of the
reaction lead to the generation of the first heterosubstituted 1-silaallenes.6,7 In this article,
we describe recent efforts to encompass the destannylation of 1.
RESULTS AND DISCUSSION
The thermal elimination behavior of phosphanostannanes 1a,b has been explored.4
Heating of the neat compounds to 200◦C under inert conditions does not lead to the
envisioned chlorostannane elimination but to destannylated hydrophosphanes 2 and 3 or
Received 16 November 2010; accepted 23 November 2010.
Financial support by the Austrian Science Fund (FWF) (P20575-N19), the Land Steiermark, and EU-COST
Action CM 0802 (PhoSciNet) is gratefully acknowledged.
Address correspondence to Rudolf Pietschnig, Institute of Chemistry, Inorganic Chemistry, Karl Franzens
University Graz, Schubertstraße 1, A-8010 Graz, Austria. E-mail: rudolf.pietschnig@uni-graz.at
1361

1362
R. PIETSCHNIG AND A. ORTHABER
Scheme 1 Elimination and complexation reactions of 1a,b(I-III) [E = Ge (a), E = Si (b); R = Cp∗ (I), Mes (II),
Tip(III)].
polymeric materials (Scheme 1). The complexation of the phosphorus center with an
Fe(CO)5 fragment leading to 4 has also been explored successfully.8
CONCLUSIONS
The thermal treatment of stannylphosphano halo-silanes and germanes leads to
destannylation under preservation of the halogen silicon/germanium bonds. The P-Sn bond
seems to be the most reactive site of these molecules.
EXPERIMENTAL
Heating of neat 1 to 200◦C under inert conditions leads to polymeric materials and
compounds 2 and 3. Relevant NMR data of 1–4 from Ref.8 are listed in Table 1.
Table 1 Selected NMR parameters of 1–4
E =
R =
Entry
δ(31P) [ppm]
1J(P-117Sn) [Hz]
1J(P-119Sn) [Hz]
1J(P-Si) [Hz]
1J(P-H) [Hz]
Ge
Si
Si
Si
Si
Si
Si
Ge
Si
Si
Si
Si
Si
Cp∗
Cp∗
Mes
Tip
1a
1bI
−242.4
−272.1
−242.5
−235.0
−261.1
−210.0
−206.0
−224.8
−228.7
−189.2
−183.0
−196.8
−195.7
718
669
681
693
538
593
—
—
—
—
—
752
721
713
725
563
621
617
—
—
—
—
304
330
—
116
99
101
96
83
—
—
41
45
43
—
—
—
—
—
1bII
1bIII
2bI
2bII
2bIII
3a
—
Cp∗
Mes
Tip
176
179
181
183
187
193
191
—
Cp∗
Cp∗
Mes
Tip
Cp∗
Mes
3bI
3bII
3bIII
4bI
—
—
4bII
—

HETERONUCLEAR TRIPLE BONDS
1363
REFERENCES
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1066–1070.
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3. Sasamori, T.; Hironaka, K.; Sugiyama, Y.; Takagi, N.; Nagase, S.; Hosoi, Y.; Furukawa, Y.;
Tokitoh, N. J. Am. Chem. Soc. 2008, 130, 13856–13857.
4. Bender, M.; Niecke, E.; Nieger, M.; Pietschnig, R. Eur. J. Inorg. Chem. 2006, 380–384.
5. Pietschnig, R.; Tirree´, J. J. In Organosilicon Chemistry—From Molecules to Materials VI; N.
Auner and J. Weis, Eds.; Wiley-VCH, Weinheim, Germany, 2005, pp. 222–227.
6. Pietschnig, R.; Scha¨fer, S. Silicon Chem. 2003, 2, 131–135.
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8. Waltz, M. Thesis, University of Bonn, Bonn, Germany, 1994.