Abstract
The reaction of silylene with acetylene was observed by the density function theory (DFT) method at the 6 - 311 g (d,p) level. A new reaction pathway has been identified involving the tetra-conjugated: SiH2CH==CHH2Si:. Thermodynamic and kinetic analysis confirms the reaction to be spontaneous at room temperature. The new intermediate proposed in this work offers a resolution of the conundrum of the silylene/acetylene reaction.
References
1.
Rubaiey N.
, and
Walsh R.
(1994 ) J. Phys. Chem. , 98 , 5303 .
2.
Moss R.A.
,
Platz M.S.
, and M.J. Jr. (2004 ) Reactive intermediate chemistry , Wiley , New York .
3.
Yamada T.
,
Mawatari A.
, and
Tanabe M.
(2009 ) Angew. Chem. Int. Ed. , 48 , 567 .
4.
Apeloig Y.
,
Pauncz R.
,
Kami M.
, and
Chapman D.
(2003 ) Organometallics , 22 , 3250 .
5.
Coombs N.D.
,
Vidovic D.
, and
Day J.K.
(2008 ) J. Am. Chem. Soc. , 130 , 16111 .
6.
Takagi N.
,
Shimizu T.
, and
Frenking G.
(2009 ) Chem. Eur. J. , 15 , 3448 .
7.
Eutziz E
,
Mix A.
,
Rummel B.
, and
Schoeller W.W.
(2004 ) Science , 305 , 849 .
8.
Molev G.
,
Bravo-Zhivotovskii D.
,
Kami M.
, and
Tumaniskii B.
(2006 ) J. Am. Chem. Soc. , 128 , 2784 .
9.
Sekiguchi A.
,
Inoue S.
, and
Ichinoe M.
(2002 ) J. Am. Chem. Soc. , 124 , 15160 .
10.
Iwamoto T.
,
Kabuto C.
, and
Kria M.
(1999 ) J. Am. Chem. Soc. , 1121 , 886 .
11.
So C.W.
,
Roesky H.W.
, and
Magull J.
(2006 ) Angew. Chem. Int. Ed. , 45 , 3948 .
12.
Atwell W.H.
(2009 ) Organometallics , 28 , 3573 .
13.
Barton T.J.
, and
Kilgour J.A.
(1974 ) J. Am. Chem. Soc. , 96 , 7150 .
14.
Barton T.J.
, and
Kilgour J.A.
(1976 ) J. Am. Chem. Soc. , 98 , 7746 .
15.
Ishikawa M.
,
Sugisawa H.
,
Kumada M.
,
Kawakami H.
, and
Yamabe T.
(1983 ) Organometallics , 2 , 974 .
16.
Gonzalez C.
, and
Schlegel H.B.
(1990 ) J. Phys. Chem. , 94 , 5523 .
17.
Frisch M.J.
,
Trucks G.W.
,
Schlegel H.B.
2003 ) Gaussian 03, Revision A.l , Gaussian Inc. , Pittsburgh PA.