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(29) If the alkyne serves as a 4-electron donor, complexes of type 9
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(47) Addition of Me3SnH (1 equiv) to a solution containing the η2-
complex 9b and a second equivalent of 8b in CD2Cl2 at −40 °C
resulted in quantitative trans-hydrostannation at the time the first
spectrum was pulsed. The η2-complex was regenerated and no
detectable free alkyne left over. In addition, traces of an unknown σ-
(30) Compare: (a) Le Paih, J.; Der
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stannane complex (δH = −8.4 ppm, JSn,H = 185 Hz) were detected.
(31) For a related [2 + 2] cycloadditon catalyzed by [Cp*Fe], see:
(48) In some cases, (EtO)3SiH afforded slightly better regioselectiv-
ities which might reflect the better acceptor properties of this reagent;
the isolated yields, however, are generally lower because the resulting
siloxanes are less stable.
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(32) The cycloadducts 10 were obtained in trace amounts even from
1:1 mixtures of complex 4 and alcohol 8, when kept at −20 °C for 2−5
days; for preparative purposes, however, 8 was used in large excess
(10−15 equiv.), see the Supporting Information.
(49) The X-ray structure of this complex is contained in the
Supporting Information; for its sibling [CpRuI(cod)], see: Perekalin,
D. S.; Karslyan, E. E.; Trifonova, E. A.; Konovalov, A. I.; Loskutova, N.
M
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX