Tebbe-like and Phosphonioalkylidene and -alkylidyne Complexes of Scandium
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https://figshare.com/articles/dataset/Tebbe-like_and_Phosphonioalkylidene_and_-alkylidyne_Complexes_of_Scandium/12360929
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资源简介：
The
bonding between scandium and carbon in a series of alkylidene- and
alkylidyne-like moieties is compared. The Tebbe analogue complex (PNP)Sc(μ2-CHSiMe3)(μ2-CH3)[Al(CH3)(CH2SiMe3)] (2) (PNP– = N[2-PiPr2-4-methylphenyl]2) could be formed by adding AlMe3 to (PNP)Sc(CH2SiMe3)2 (1). The fluxional behavior of 2 is studied by
a combination of 2D 13C–1H HMQC, HMBC,
and other heteronuclear NMR spectroscopic experiments. The phosphonioalkylidene
complex (PNP)Sc(CHPPh3)(CH3) (3) could be prepared from 2 by treatment with 2 equiv
of the ylide H2CPPh3 or by methane elimination
from (PNP)Sc(CH3)2 and 1 equiv of H2CPPh3. The reactivity of the alkylidene in 2 was further explored with N3Ad, which gave insertion
at the Sc–C bond, yielding (PNP)Sc(CH3)[η2-N3AdCHSiMe3Al(CH3)(CH2SiMe3)] (4), while DMAP provided C–H
activation across the alkylidene with loss of the Al–C bond
to form (PNP)Sc(η2-NC5H3NMe2)(CH2SiMe3) (5). Utilizing
the same approach that yielded 2, methane elimination
in 3 could further be promoted with Al(CH3)3 to furnish the first example of a scandium phosphonioalkylidyne
complex, (PNP)Sc(μ2-CPh3)(μ2-CH3)Al(CH3)2 (6). Experimental and theoretical studies were combined to compare
the bonding in 2, 3, and 6,
in order to understand the legitimacy of Sc–C multiple bond
character.
创建时间：
2020-04-21
