TY - JOUR
T1 - Reactions of a Silylyne Complex with Aldehydes
T2 - Formation of W−Si−O−C Four-Membered Metallacycles and Their Metathesis-Like Fragmentation
AU - Yoshimoto, Takashi
AU - Hashimoto, Hisako
AU - Takagi, Nozomi
AU - Sakaki, Shigeyoshi
AU - Hayakawa, Naoki
AU - Matsuo, Tsukasa
AU - Tobita, Hiromi
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers JP15H03782 and JP15K05444), and a Grant-in-Aid for Scientific Research on Innovative Areas, “Stimuli-responsive Chemical Species for the Creation of Functional Molecules” [#2408] (JSPS KAKENHI Grant Numbers. JP24109003 and JP24109011). We thank the Research Center for Computational Science of Institute for Molecular Science (IMS, Okazaki, Japan) for kindly allowing us to use computers. We also thank Rigaku Corporation (Japan) for the X-ray crystal structure analysis of cis-7c.
Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers JP15H03782 and JP15K05444), and a Grant-in-Aid for Scientific Research on Innovative Areas, ?Stimuli-responsive Chemical Species for the Creation of Functional Molecules? [#2408] (JSPS KAKENHI Grant Numbers. JP24109003 and JP24109011). We thank the Research Center for Computational Science of Institute for Molecular Science (IMS, Okazaki, Japan) for kindly allowing us to use computers. We also thank Rigaku Corporation (Japan) for the X-ray crystal structure analysis of cis-7 c.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/3/12
Y1 - 2019/3/12
N2 - A tungsten silylyne complex having a W≡Si triple bond reacted with two molecules of aldehydes at room temperature to give W−Si−O−C four-membered metallacycles by [2+2] cycloaddition and subsequent formyl hydrogen transfer from one aldehyde molecule to another. Upon heating to 70 °C, the four-membered metallacycles underwent metathesis-like fragmentation cleanly to afford carbyne complexes and “silanoic esters,” in a manner similar to that of metallacyclobutadiene, an intermediate of alkyne metathesis reactions, and dimerization of the latter products gave 1,3-cyclodisiloxanes. The “silanoic ester” was also trapped by pivalaldehyde to give a [2+2] cycloaddition product in high yield.
AB - A tungsten silylyne complex having a W≡Si triple bond reacted with two molecules of aldehydes at room temperature to give W−Si−O−C four-membered metallacycles by [2+2] cycloaddition and subsequent formyl hydrogen transfer from one aldehyde molecule to another. Upon heating to 70 °C, the four-membered metallacycles underwent metathesis-like fragmentation cleanly to afford carbyne complexes and “silanoic esters,” in a manner similar to that of metallacyclobutadiene, an intermediate of alkyne metathesis reactions, and dimerization of the latter products gave 1,3-cyclodisiloxanes. The “silanoic ester” was also trapped by pivalaldehyde to give a [2+2] cycloaddition product in high yield.
KW - [2+2] cycloaddition
KW - aldehyde
KW - metathesis-like fragmentation
KW - silylyne complex
KW - tungsten
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U2 - 10.1002/chem.201900457
DO - 10.1002/chem.201900457
M3 - Article
C2 - 30706971
AN - SCOPUS:85061937567
VL - 25
SP - 3795
EP - 3798
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 15
ER -