US 8,299,284 B2 · Frustrated lewis pair compositions

Abstract

A compound having the formula (I) where each of R1, R2, R3 and R4 is independently C6-C18 aryl-, C5-C8 cycloalkyl-, C6-C18 aryl having at least one C1-C20 alkyl substituent, C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent, C4-C20 branched alkyl-, C16-C20 linear alkyl-, RO—, —NRR′, —PRR′, —SR, fluoro substituted forms thereof, and perfluoro forms thereof: and R5 is C6-C18 aryl-, C5-C8 cycloalkyl-, C6-C18 aryl having at least one C1-C20 alkyl substituent, C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent, C3-C20 branched alkyl-, C2-C30 linear alkyl-, fluoro substituted forms thereof, and perfluoro forms thereof; where R and R′ are each independently C6-C18aryl-, C5-C8 cycloalkyl-, C6-C18 aryl having at least one C1-C20 alkyl substituent, C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent, C4-C20 branched alkyl-, C2-C30 linear alkyl-, fluoro substituted forms thereof, and perfluoro forms thereof; A is N, P, S, or O with the proviso that when A is S, R2 is a nullify; and M is B, Al, Ga or In.

Claims62

Dependent claims

A compound comprising:

a sterically hindered Lewis acid comprising B, Al, Ga, In, Ti, Zr or Hf;
a sterically hindered Lewis base comprising N, P, S, or O;
and
an intermediate linker group therebetween.

1 more element

A process comprising dissociating an addition reaction reagent by combining the reagent and:

(i) a compound of formula I;
(ii) a compound of formula IV;
(iii) a mixture of a compound of formula II in fluid communication with a compound of formula III;
or
(iv) a compound of formula III, to form a catalyst,
wherein the compounds of formula I and IV are
where
R1, R2, R3 and R4 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R5 is:
C6-C18 arylene;
C5-C8 cycloalkanediyl;
C6-C18 arylene having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkanediyl having at least one C1-C20 alkyl substituent;
C3-C20 branched alkanediyl;
or C2-C30 linear alkanediyl;
R and R′ are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
or C2-C30 linear alkyl;
A is:
N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is:
B;
Al;
Ga;
or In,
and wherein the compounds of formula II and III are
wherein
R1, R2, R4, R5 and R7 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R6 is C1-C30 alkyl;
C6-C18 aryl;
C5-C8 cycloalkyl;
—OR;
—NRR′;
—PRR′;
—SR;
H;
or F;
R and R′ are each, independently:
C6-C18 aryl-;
C5-C8 cycloalkyl-;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl-;
or C2-C30 linear alkyl-;
A is N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is B, Al, Ga or In.

77 more elements

A process comprising:

providing in a reaction vessel a compound or mixture selected from:
a compound of formula I;
a compound of formula III;
a compound of formula IV;
a mixture of a compound of formula II and a compound of formula III;
a mixture of a compound of formula II and a compound of formula I;
or
a mixture of a compound of formula II and a compound of formula IV;
and
a substrate;
charging the reaction vessel with dihydrogen;
forming a catalyst;
reacting to form a reduction product that is a hydrogenated form of the substrate;
and
obtaining the reduction product;
wherein, when the compound or mixture is a compound of formula III, the substrate comprises N, P, S, or O,
wherein the compounds of formula I and IV are
where
R1, R2, R3 and R4 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R5 is:
C6-C18 arylene;
C5-C8 cycloalkanediyl;
C6-C18 arylene having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkanediyl having at least one C1-C20 alkyl substituent;
C3-C20 branched alkanediyl;
or C2-C30 linear alkanediyl;
R and R′ are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
or C2-C30 linear alkyl;
A is:
N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is:
B;
Al;
Ga;
or In,
and wherein the compounds of formula II and III are
wherein
R1, R2, R4, R5 and R7 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R6 is C1-C30 alkyl;
C6-C18 aryl;
C5-C8 cycloalkyl;
—OR;
—NRR′;
—PRR′;
—SR;
H;
or F;
R and R′ are each, independently:
C6-C18 aryl-;
C5-C8 cycloalkyl-;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl-;
or C2-C30 linear alkyl-;
A is N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is B, Al, Ga or In.

88 more elements

A process for dissociating dihydrogen and reversibly binding hydrogen atoms to at least one molecule, comprising exposing dihydrogen, under conditions that induce binding, to:

(i) a compound comprising a sterically hindered Lewis acid comprising B, Al, Ga, In, Ti, Zr or Hf;
a sterically hindered Lewis base comprising N, P, S, or O;
and an intermediate linker group therebetween;
(ii) a compound of formula I;
(iii) a compound of formula IV;
(iv) a composition comprising a first compound comprising a sterically hindered Lewis acid;
and a second compound comprising a sterically hindered Lewis base;
wherein the Lewis acid comprises B, Al, Ga, In, Ti, Zr or Hf, and wherein the Lewis base comprises N, P, S, or O;
(v) a compound of formula II in fluid communication with a compound of formula III;
or
(vi) a compound of formula IIa in fluid communication with a compound of formula V, where the compounds of formula I or formula IV are
where
R1, R2, R3 and R4 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R5 is:
C6-C18 arylene;
C5-C8 cycloalkanediyl;
C6-C18 arylene having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkanediyl having at least one C1-C20 alkyl substituent;
C3-C20 branched alkanediyl;
or C2-C30 linear alkanediyl;
R and R′ are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
or C2-C30 linear alkyl;
A is:
N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is:
B;
Al;
Ga;
or In,
where the compounds of formulas II and III are
where
R1, R2, R4, R5 and R7 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R6 is C1-C30 alkyl;
C6-C18 aryl;
C5-C8 cycloalkyl;
—OR;
—NRR′;
—PRR′;
—SR;
H;
or F;
R and R′ are each, independently:
C6-C18 aryl-;
C5-C8 cycloalkyl-;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl-;
or C2-C30 linear alkyl-;
A is N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is B, Al, Ga or In,
and where the compounds of formulas IIa and V are
where
R1 and R2 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R6 is C1-C30 alkyl;
C6-C18 aryl;
C5-C8 cycloalkyl;
—OR;
—NRR′;
—PRR′;
—SR;
H;
or F;
R8, R9, and R10 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
amide;
alkoxide;
phenoxide;
phosphinimide;
cyclopentadienyl;
indenyl;
fluorenyl derivatives;
—OR;
—NRR′;
—PRR′;
or —SR;
R11 is C1-C20 alkyl linear or branched with the proviso that R11 is a better leaving group than any of R8, R9 or R10 under nucleophic attack by a hydrogen or other alkyl abstracting agents to yield a cationic M1 species;
R and R′ are each, independently:
C6-C18 aryl-;
C5-C8 cycloalkyl-;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl-;
or C2-C30 linear alkyl-;
A is N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M1 is Ti, Zr or Hf.

136 more elements

A process for preparing an addition reaction product of a substrate, comprising catalyzing a reaction of a substrate and an addition reaction reagent by combining the substrate and the addition reaction reagent with:

(i) a compound of formula I;
(ii) a compound of formula IV;
(iii) a mixture of a compound of formula II in fluid communication with a compound of formula III;
or
(iv) a compound of formula III,
wherein the compounds of formula I and IV are
where
R1, R2, R3 and R4 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R5 is:
C6-C18 arylene;
C5-C8 cycloalkanediyl;
C6-C18 arylene having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkanediyl having at least one C1-C20 alkyl substituent;
C3-C20 branched alkanediyl;
or C2-C30 linear alkanediyl;
R and R′ are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
or C2-C30 linear alkyl;
A is:
N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is:
B;
Al;
Ga;
or In,
and wherein the compounds of formula II and III are
wherein
R1, R2, R4, R5 and R7 are, independently:
C6-C18 aryl;
C5-C8 cycloalkyl;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl;
C16-C30 linear alkyl;
—OR;
—NRR′;
—PRR′;
or —SR;
R6 is C1-C30 alkyl;
C6-C18 aryl;
C5-C8 cycloalkyl;
—OR;
—NRR′;
—PRR′;
—SR;
H;
or F;
R and R′ are each, independently:
C6-C18 aryl-;
C5-C8 cycloalkyl-;
C6-C18 aryl having at least one C1-C20 alkyl substituent;
C5-C8 cycloalkyl having at least one C1-C20 alkyl substituent;
C4-C20 branched alkyl-;
or C2-C30 linear alkyl-;
A is N;
P;
S;
or O;
with the proviso that when A is S or O, R2 is a nullity;
and
M is B, Al, Ga or In.

77 more elements

Dependencies are inferred from the claim text.

Frustrated lewis pair compositions

Life of this patent

Frustrated lewis pair compositions

Life of this patent

Abstract

Claims62