The Chemistry of Disilyne with a Genuine Si–Si Triple Bond: Synthesis, Structure, and Reactivity

Abstract

In this account, our recent results on the chemistry of a stable silicon-silicon triply-bonded compound, disilyne, including recent advances in the chemistry of stable alkyne analogues of heavier group 14 elements, are described. Our original extremely bulky trialkylsilyl substituent, Dis 2 i PrSi [Dis = CH(SiMe 3 ) 2 ], has enabled the isolation of disilyne as a stable compound, which has been completely characterized by various spectroscopic techniques, as well as X-ray crystallography. Some reactivity of our isolable disilyne will be discussed.

Structure and Reactions of an Isolable Ge=Si Doubly Bonded Compound, Tetra(t-butyldimethylsilyl)germasilene

“…Synthesis and structure of stable unsaturated compounds of heavy group-14 elements is one of the primary subjects of both experimental and theoretical main-group element chemistry; see reviews of experimental [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] and theoretical aspects [20][21][22][23][24]. Since the first synthesis of stable digermenes and distannenes by Lappert et al [25][26][27] and a stable disilene by West et al [28], a number of heavy alkenes (R 2 E=ER 2 , E, E' = Si, Ge, Sn, and Pb) have been synthesized and their unusual structures and properties have been revealed.…”

Silicon version of enamines: Amino-substituted disilenes by the reactions of the disilyne RSi SiR (R = Si Pr[CH(SiMe3)2]2) with amines

“…Although amino-substituted disilenes 2a, 2c, and 2d did not react with excess amine because of their steric hindrance, the smallest pyrrolidino group-substituted disilene 2b reacted with a second pyrrolidine molecule to afford 3 in 85% yield (Scheme 1). This reaction is similar to the reaction of disilyne 1 with alcohols, which only gives 1,1-dialkoxydisilanes [25].…”

Disilyne with a silicon-silicon triple bond: A new entry to multiple bond chemistry

“…However, the chemistry of disilyne with a silicon-silicon triple bond was missing until reports in 2004 by our group and Wiberg [9,10]. We present here the synthesis and structural characterization of a disilyne with a new type of π bond, as well as its reactivity [9,11].…”