Gehrhus, Barbara; Hitchcock, Peter B.; Lappert, Michael F.; Heinicke, Joachim; Boese, Roland; Blaeser, Dieter:

Synthesis, structures and oxidative addition reactions of new thermally stable silylenes; crystal structures of chelates [Si{N(CH2tBu)}2C6H4-1,2] and [(Si{N(CH2tBu)}2C6H4-1,2)(m-E)]2 (E = Se or Te).

In: Journal of Organometallic Chemistry, Jg. 521 (1996) ; Nr. 1-2, S. 211-220
ISSN: 0022-328X
Zeitschriftenaufsatz / Fach: Chemie
Successive treatment of N,N'-dineopentyl-1,2-phenylenediamine 4-RC6H3[NH(CH2tBu)]2-1,2 (R = H or Me) with 2 equiv BuLi and 1 equiv SiCl4 yields the appropriate N,N'-dineopentyl-1,2-phenylenediaminodichlorosilane Si[{N(CH2tBu)}2C6H3-1,2-R-4]Cl2 [R = H (1) or Me (2)]. The thermally stable, yellow, diamagnetic, volatile, cryst. silylenes Si[{N(CH2tBu)}2C6H3-1,2-R-4] [R = H (3) or Me (4)] were obtained from 1 or 2, resp., by reaction with K in refluxing THF. Silylene 3 undergoes oxidative addn. with (i) MeI or EtOH to give [Si{N(CH2tBu)}2C6H4-1,2](X)Y [X = Me, Y = I (5); X = OEt, Y = H (6)], or (ii) a chalcogen E to afford [(Si{N(CH2tBu)}2C6H4-1,2)(m-E)]2 [E = S (7), Se (8) or Te (9)]. Spectroscopic data are provided for compds. 1-9 and single crystal x-ray diffraction results are given for 3, 8 and 9. The av. Si-N distances are 1.750(4) .ANG. for the silylene 3, 1.719(4) .ANG. for the cyclodisilaselenane 8, and 1.729(3) .ANG. for the cyclodisilatellurane 9, with N-Si-N' angles being 88.2(1) Deg for 3, 93.5(2) Deg for 8, and 93.7(1) Deg for 9.

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