22 research outputs found
Extremely Bulky Amido First Row Transition Metal(II) Halide Complexes: Potential Precursors to Low Coordinate Metal–Metal Bonded Systems
No full textReactions
of the extremely bulky potassium amide complexes, [KL′(η<sup>6</sup>-toluene)] or [KL″] (L′/L″ = N(Ar*)(SiR<sub>3</sub>), Ar* = C<sub>6</sub>H<sub>2</sub>{C(H)Ph<sub>2</sub>}<sub>2</sub>Me-2,6,4; R = Me (L′) or Ph (L″)), with a series
of first row transition metal(II) halides have yielded 10 rare examples
of monodentate amido first row transition metal(II) halide complexes,
all of which were crystallographically characterized. They encompass
the dimeric, square-planar chromium complexes, [{CrL′(THF)(μ-Cl)}<sub>2</sub>] and [{CrL″(μ-Cl)}<sub>2</sub>], the latter
of which displays intramolecular η<sup>2</sup>-Ph···Cr
interactions; the dimeric tetrahedral complexes, [{ML′(THF)(μ-Br)}<sub>2</sub>] (M = Mn or Fe), [{ML″(THF)(μ-X)}<sub>2</sub>] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL″(μ-Cl)}<sub>2</sub>] (which displays intramolecular η<sup>2</sup>-Ph···Co
interactions); and the monomeric zinc amides, [L′ZnBr(THF)]
(three-coordinate) and [L″ZnBr] (two-coordinate). Solution
state magnetic moment determinations on all but one of the paramagnetic
compounds show them to be high-spin systems. Throughout, comparisons
are made with related bulky terphenyl transition metal(II) halide
complexes, and the potential for the use of the prepared complexes
as precursors to low-valent transition metal systems is discussed
Extremely Bulky Amido First Row Transition Metal(II) Halide Complexes: Potential Precursors to Low Coordinate Metal–Metal Bonded Systems
No full textReactions
of the extremely bulky potassium amide complexes, [KL′(η<sup>6</sup>-toluene)] or [KL″] (L′/L″ = N(Ar*)(SiR<sub>3</sub>), Ar* = C<sub>6</sub>H<sub>2</sub>{C(H)Ph<sub>2</sub>}<sub>2</sub>Me-2,6,4; R = Me (L′) or Ph (L″)), with a series
of first row transition metal(II) halides have yielded 10 rare examples
of monodentate amido first row transition metal(II) halide complexes,
all of which were crystallographically characterized. They encompass
the dimeric, square-planar chromium complexes, [{CrL′(THF)(μ-Cl)}<sub>2</sub>] and [{CrL″(μ-Cl)}<sub>2</sub>], the latter
of which displays intramolecular η<sup>2</sup>-Ph···Cr
interactions; the dimeric tetrahedral complexes, [{ML′(THF)(μ-Br)}<sub>2</sub>] (M = Mn or Fe), [{ML″(THF)(μ-X)}<sub>2</sub>] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL″(μ-Cl)}<sub>2</sub>] (which displays intramolecular η<sup>2</sup>-Ph···Co
interactions); and the monomeric zinc amides, [L′ZnBr(THF)]
(three-coordinate) and [L″ZnBr] (two-coordinate). Solution
state magnetic moment determinations on all but one of the paramagnetic
compounds show them to be high-spin systems. Throughout, comparisons
are made with related bulky terphenyl transition metal(II) halide
complexes, and the potential for the use of the prepared complexes
as precursors to low-valent transition metal systems is discussed
Low-Coordinate Cobalt(I) Complexes Stabilized by an Extremely Bulky Amide Ligand
No full textA series of low-coordinate, high-spin,
mono- and dinuclear cobalt(I) complexes bearing an extremely bulky
amide (L″ = N(Ar*)(SiPh<sub>3</sub>); Ar* = C<sub>6</sub>H<sub>2</sub>{C(H)Ph<sub>2</sub>}<sub>2</sub>Me-2,6,4) ligand have been
synthesized and characterized. These include the first example of
a neutral two-coordinate cobalt(I) complex, [L″Co(IPriMe)]
(IPriMe = :C{N(Pr<sup><i>i</i></sup>)C(Me)}<sub>2</sub>),
which has a near-linear cobalt coordination geometry
Reversible, Room-Temperature CC Bond Activation of Benzene by an Isolable Metal Complex
No full textThe
activation of CC bonds is of fundamental interest in
the construction of complex molecules from petrochemical feedstocks.
In the case of the archetypal aromatic hydrocarbon benzene, CC
cleavage is thermodynamically disfavored, and is brought about only
by transient highly reactive species generated in situ. Here we show that the oxidative addition of the CC bond
in benzene by an isolated metal complex is not only possible, but
occurs at room temperature and reversibly at a single aluminium center
in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over CH
bond activation is achieved kinetically and allows for the generation
of functionalized acyclic products from benzene
Reversible, Room-Temperature CC Bond Activation of Benzene by an Isolable Metal Complex
No full textThe
activation of CC bonds is of fundamental interest in
the construction of complex molecules from petrochemical feedstocks.
In the case of the archetypal aromatic hydrocarbon benzene, CC
cleavage is thermodynamically disfavored, and is brought about only
by transient highly reactive species generated in situ. Here we show that the oxidative addition of the CC bond
in benzene by an isolated metal complex is not only possible, but
occurs at room temperature and reversibly at a single aluminium center
in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over CH
bond activation is achieved kinetically and allows for the generation
of functionalized acyclic products from benzene
Reversible, Room-Temperature CC Bond Activation of Benzene by an Isolable Metal Complex
No full textThe
activation of CC bonds is of fundamental interest in
the construction of complex molecules from petrochemical feedstocks.
In the case of the archetypal aromatic hydrocarbon benzene, CC
cleavage is thermodynamically disfavored, and is brought about only
by transient highly reactive species generated in situ. Here we show that the oxidative addition of the CC bond
in benzene by an isolated metal complex is not only possible, but
occurs at room temperature and reversibly at a single aluminium center
in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over CH
bond activation is achieved kinetically and allows for the generation
of functionalized acyclic products from benzene
Reversible, Room-Temperature CC Bond Activation of Benzene by an Isolable Metal Complex
No full textThe
activation of CC bonds is of fundamental interest in
the construction of complex molecules from petrochemical feedstocks.
In the case of the archetypal aromatic hydrocarbon benzene, CC
cleavage is thermodynamically disfavored, and is brought about only
by transient highly reactive species generated in situ. Here we show that the oxidative addition of the CC bond
in benzene by an isolated metal complex is not only possible, but
occurs at room temperature and reversibly at a single aluminium center
in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over CH
bond activation is achieved kinetically and allows for the generation
of functionalized acyclic products from benzene
Reversible, Room-Temperature CC Bond Activation of Benzene by an Isolable Metal Complex
No full textThe
activation of CC bonds is of fundamental interest in
the construction of complex molecules from petrochemical feedstocks.
In the case of the archetypal aromatic hydrocarbon benzene, CC
cleavage is thermodynamically disfavored, and is brought about only
by transient highly reactive species generated in situ. Here we show that the oxidative addition of the CC bond
in benzene by an isolated metal complex is not only possible, but
occurs at room temperature and reversibly at a single aluminium center
in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over CH
bond activation is achieved kinetically and allows for the generation
of functionalized acyclic products from benzene
Reversible, Room-Temperature CC Bond Activation of Benzene by an Isolable Metal Complex
No full textThe
activation of CC bonds is of fundamental interest in
the construction of complex molecules from petrochemical feedstocks.
In the case of the archetypal aromatic hydrocarbon benzene, CC
cleavage is thermodynamically disfavored, and is brought about only
by transient highly reactive species generated in situ. Here we show that the oxidative addition of the CC bond
in benzene by an isolated metal complex is not only possible, but
occurs at room temperature and reversibly at a single aluminium center
in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over CH
bond activation is achieved kinetically and allows for the generation
of functionalized acyclic products from benzene
Reversible, Room-Temperature CC Bond Activation of Benzene by an Isolable Metal Complex
No full textThe
activation of CC bonds is of fundamental interest in
the construction of complex molecules from petrochemical feedstocks.
In the case of the archetypal aromatic hydrocarbon benzene, CC
cleavage is thermodynamically disfavored, and is brought about only
by transient highly reactive species generated in situ. Here we show that the oxidative addition of the CC bond
in benzene by an isolated metal complex is not only possible, but
occurs at room temperature and reversibly at a single aluminium center
in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over CH
bond activation is achieved kinetically and allows for the generation
of functionalized acyclic products from benzene
