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US 6,909,009 B2Granted
Alkane and alkane group dehydrogenation with organometallic catalysts
OwnerAvtandil Koridzeinventor
Life of this patent
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Abstract
Novel polynuclear organometallic complexes useful as catalysts for the reversible deshydrogenation of alkanes and alkane group are disclosed. The novel compounds comprise a first transition, a second transition metal p-bonded to an ?5-aromatic ligand, and a pincer ligand. The pincer ligand comprises a 6p-electron aromatic ring having at least 2 ring atoms in an 1, 3 relationship bonded each to a neutral Lewis base through a bridge, the bridge being a diradical. The pincer ligand binds the first transition metal through each of the Lewis bases and through the ring atom adjacent to both Lewis bases and p-coordinates the second transition metal through all aromatic ring atoms. The first transition metal may also bond to 2 or 4 hydrogen atoms.
Claims22
A polynuclear organometallic compound comprising a tripodal pincer ligand comprising at least one aromatic ring and two neutral Lewis bases, said Lewis bases being indirectly linked to said aromatic ring through a bridge, said pincer ligand coordinating to a first transition metal through each of the Lewis bases and having one atom σ-bonded to said first transition metal, the aromatic ring of said pincer ligand having all ring atoms π-bonded to a second transition metal.
A polynuclear organometallic compound comprising:
- (a) a first transition metal selected from the group consisting of Rh, Ir, said first transition metal being bonded to n hydrogen atoms, n being an integer selected such that first transition metal has an electron count of 16 or 18 electrons;
- (b) a second transition metal selected from the group consisting of Fe, Ru, Rh, Os, and Ir, said second transition metal being π-bonded to an η5-aromatic ligand;
- (c) a pincer ligand comprising a 6π-electron aromatic ring having at least 2 ring atoms in an 1,3 relationship bonded each to a neutral Lewis base through a bridge, L1 and L2 independently of one another are —PR′R″, As R′R″ or —Sb R′R″;
- wherein R′ and R″ independently of one another are wherein R′ and R″ independently of one another are an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 and R2 independently of one another are hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms;
- a is the number of substituents R1 and is ranging from 0 to 2 inclusive;
- b is the number of substituents R2 and is ranging from 0 to 5 inclusive;
- n is an integer equal to 2 when M is Rh and equal to 2 or 4 when M is Ir;
- q is an integer ranging from 0 to 1 depending on the oxidation state of M′;
- and said bridge being a diradical, and said pincer ligand binding the first transition metal through each of the Lewis base and through the ring atom adjacent to both lewis bases and having all aromatic ring atoms π-coordinated to the second transition metal through all of the aromatic ring atoms.
8 more elements
A binuclear organometallic compound of formula (I):
- wherein:
- M is Rh, Ir;
- M′ is Fe, Ru, Rh, Os, or Ir;
- L1 and L2 independently of one another are —PR′R″AsR′ R″ or —Sb R′R″;
- wherein R′ and R″ independently of one another are wherein R′ and R″ independently of one another are an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 and R2 independently of one another are hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms;
- a is the number of substituents R1 and is ranging from 0 to 3 inclusive;
- b is the number of substituents R2 and is ranging from 0 to 5 inclusive;
- n is an integer equal to 2 when M is Rh and equal to 2 or 4 when M is Ir;
- q is an integer equal to 1 when M is Fe, Ru or Os and equal to 2 when M′ is Rh or Ir;
- and
- Y is a counter anion that provides the required charge balance.
10 more elements
A binuclear organometallic compound of formula (II):
- wherein:
- M is Rh, Ir;
- M′ is Fe, Ru, Os;
- Y is a counter anion that provides the required charge balance.
1 more element
A trinuclear organometallic compound of formula III:
- wherein:
- M is Rh, Ir;
- M′ is Fe, Ru, Os;
- L1 and L2 independently of one another are —PR′R″, AsR′R″ or —SbR′R″;
- wherein R′ and R″ independently of one another are wherein R′ and R″ independently of one another are an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 is hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms;
- a is the number of substituents R1 and is ranging from 0 to 2 inclusive;
- n is an integer equal to 2 when M is Rh and equal to 2 or 4 when M is Ir;
- q is an integer ranging from 0 to 1 depending on the oxidation state of M′;
- and
- Y is a counter anion that provides the required charge balance.
9 more elements
A mononuclear complex of formula V:
- wherein:
- M′ is Fe, Ru, Os;
- L1 and L2 independently of one another are —PR′R″, AsR′R″ or —SbR′R″;
- wherein R′ and R″ independently of one another are optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 and R2 independently of one another are hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms;
- a is the number of substituents R1 and is ranging from 0 to 2 inclusive;
- b is the number of substituents R2 and is ranging from 0 to 5 inclusive.
5 more elements
A mononuclear complex of formula VI:
- wherein:
- M′ is Fe, Ru, Os;
- L1 and L2 independently of one another are —PR′R″, AsR′R″ or —SbR′R″;
- wherein R′ and R″ independently of one another are wherein R′ and R″ independently of one another are an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 is hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2 s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms.
3 more elements
A method of using a polynuclear organometallic compound comprising the steps of
- (a) providing a polynuclear organometallic compound comprising a tripodal pincer ligand comprising at lest one aromatic ring and two neutral Lewis bases, said Lewis bases being indirectly linked to said aromatic ring through a bridge, said pincer ligand coordinating to a first transition metal through each of the Lewis bases and having one atom σ-band to said first transition metal, the aromatic ring of said pincer ligand having all ring atoms π-bonded to a second transition metal;
- and
- (b) using the compound of step (a) to cyclically store and release hydrogen.
A process for the preparation of a binuclear organometallic compound of formula (I):
- wherein:
- M is Rh, 1r
- M′ is Fe, Ru, Rh, Os, or Ir;
- L1 and L2 independently of one another are —PR′R″, AsR′R″ or —Sb R′R″;
- wherein R′ and R″ independently of one another are wherein R′ and R″ independently of one another are an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 and R2 independently of one another are hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms;
- a is the number of substituents R1 and is ranging from 0 to 3 inclusive;
- b is the number of substituents R2 and is ranging from 0 to 5 inclusive;
- n is an integer equal to 2 when M is Rh and equal to 2 or 4 when M is Ir;
- q is an integer equal to 1 when M is Fe, Ru or Os and equal to 2 when M′ is Rh or lr and
- Y is a counter anion that provides the required charge balance
- Said process comprising reacting in a solvent a mononuclear complex of formula (IV):
- wherein:
- M is Rh, or Ir;
- L1 and L2 independently of one another are —PR′R″, AsR′R″ or —SbR′R″;
- wherein R′ and R″ independently of one another are wherein R′ and R″ independently of one another are an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 and R2 independently of one another are hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms;
- a is the number of substituents R1 and is ranging from 0 to 3 inclusive
- n is an integer equal to 2 when M is Rh and equal to 2 or 4 when M is Ir;
- with a source of (Ar)M′ wherein M′ is defined as previously and Ar is a R2b substituted η5-cyclopentadienyl ligand π-bonded to M′ where R2 and b are defined as previously.
19 more elements
A process for the preparation of a binuclear organometallic compound of formula (I):
- wherein:
- M is Rh, Ir;
- M′ is Fe, Ru, Rh, Os, or Ir;
- L1 and L2 independently of one another are —PR′R″, AsR′R″ or —Sb R′R″;
- wherein R′ and R″ independently of one another are wherein R′ and R″ independently of one another are an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, or heteroaryl;
- each bridge is the same or different and is a diradical;
- R1 and R2 independently of one another are hydrogen, optionally substituted C1-C4 alkyl, alkylsilyl in which the alkyl chains contain 1 or 2 carbons, optionally substituted arylalkyl or heteroarylalkyl in which the alkyl chain contains 1 to 4 carbons, optionally substituted aryl or heteroaryl and where R1s and R2s may be the same or different and when ortho to each other can together form a saturated, unsaturated or aromatic cyclic structure which can be substituted and contain heteroatoms;
- a is the number of substituents R1 and is ranging from 0 to 3 inclusive;
- b is the number of substituents R2 and is ranging from 0 to 5 inclusive;
- n is an integer equal to 2 when M is Rh and equal to 2 or 4 when M is Ir;
- q is an integer equal to 1 when M is Fe, Ru or Os and equal to 2 when M′ is Rh or Ir;
- and
- Y is a counter anion that provides the required charge balance
- said process comprising reacting In a solvent under inert atmosphere a mononuclear complex of the formula HnM{C6R13-2,6(CH2PR2)2}, wherein M is Ir or Rh;
- R1 is H or CH3;
- n is 2 when M is Rh and 2 or 4 when M is Ir, and R is tert-butyl, isopropyl, or cyclohexyl with a source of M′{η5-C5(CH3)5}.
13 more elements
Dependencies are inferred from the claim text.