Metal N-aminoguanidinate complexes for use in thin film fabrication and catalysis

Patent metadata

Field	Value
Publication number	US-10093687-B2
Application number	US-201515529390-A
Country	US
Kind code	B2
Filing date	Nov 25, 2015
Priority date	Nov 28, 2014
Publication date	Oct 9, 2018
Grant date	Oct 9, 2018

Abstract

The present patent application relates to new metal complexes having at least one N-aminoguanidinate ligand. The patent application further relates to the preparation of the new metal complexes and also to their use. The new metal complexes are especially suitable as precursors for the preparation of functional layers by means of gas-phase thin-film processes such as CVD, MO-CVD, MOVPE and ALD. Additionally, they are also suitable as catalysts for olefin hydroamination and for olefin polymerization.

First claim

The invention claimed is:

1. Metal complex having at least one N-aminoguanidinate ligand, wherein this metal complex is of the following formula 1a or 1b

wherein
M is a metal selected from the groups 1 to 15 of the Periodic Table of the Elements (PTE), lanthanides or actinides,
R 1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, NH 2 , NH(CH 3 ), N(CH 3 ) 2 , N(C 2 H 5 ) 2 or N-pyrrolidinyl, or R 1 and R 2 together with the nitrogen atom they are bonded to form a pyrrolidinyl ring;
R 2 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, or R 2 and R 1 together with the nitrogen atom they are bonded to form a pyrrolidinyl ring;
R 3 is hydrogen, CH 3 , C 2 H 5 , NH 2 , NH(CH 3 ), N(CH 3 ) 2 , N(C 2 H 5 ) 2 N-pyrrolidinyl or a SiMe 3 group,
R 4 and R 5 independently of one another are hydrogen or a linear or branched alkyl radical having up to 4 carbon atoms, or R 4 and R 5 together with the nitrogen atom they are bonded to form a pyrrolidinyl ring;
X is a monoanionic co-ligand selected from the hydride anion (H − ), from the group of the halides, from the group of the cyclic, linear or branched alkylides having up to 8 carbon atoms, from the group of substituted or unsubstituted arylides and heteroarylides having up to 10 C atoms, from the group of alkoxylato ligands, from the group of alkylthiolato or alkylselenolato ligands or from the group of secondary amido ligands,
Y is a dianionic coligand selected from the oxo group [O] 2− , the sulfido group [S] 2− or the imido group [NR 6 ] 2− , where R 6 is a cyclic, branched or linear alkyl having up to 8 carbon atoms or is a substituted or unsubstituted aryl having up to 20 carbon atoms,
L is a neutral 2-electron donor ligand,
a is an integer between 1 and 4 and
n, m, and p each independently of one another are 0, 1, 2, 3 or 4.

2. Metal complex according to claim 1 , wherein
M is a metal selected from the groups 1 to 15 of the Periodic Table of the Elements (PTE), lanthanides or actinides,
R 1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
R 2 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms, NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
R 3 is hydrogen, CH 3 , C 2 H 5 , NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
R 4 and R 5 independently of one another are hydrogen or a linear or branched alkyl radical having up to 4 carbon atoms,
X is a monoanionic co-ligand selected from the hydride anion (H − ), from the group of the halides, from the group of the cyclic, linear or branched alkylides having up to 8 carbon atoms, from the group of substituted or unsubstituted arylides and heteroarylides having up to 10 C atoms, from the group of alkoxylato ligands, from the group of alkylthiolato or alkylselenolato ligands or from the group of secondary amido ligands,
Y is a dianionic coligand selected from the oxido group [O] 2− or the imido group [NR 6 ] 2− , where R 6 is a cyclic, branched or linear alkyl having up to 8 carbon atoms or is a substituted or unsubstituted aryl having up to 20 carbon atoms,
L is a neutral 2-electron donor ligand,
a is an integer between 1 and 4 and
n, m, and p each independently of one another are 0, 1, 2, 3 or 4.

3. Metal complex according to claim 1 , wherein
R 1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms,
R 2 is hydrogen or a cyclic, linear or branched alkyl radical having up to 5 carbon atoms,
R 3 is hydrogen, CH 3 , C 2 H 5 , NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
R 4 and R 5 are independently of one another hydrogen or a linear or branched alkyl radical having up to 3 carbon atoms,
X is the hydride anion (H − ), methylide (CH 3 − ), ethylide (C 2 H 5 − ), isopropylide (iso-C 3 H 7 − ), tert-butylide (tert-C 4 H 9 − ), the phenylide anion (C 6 H 5 − ), the ortho-, meta-, or para-tolylide anion [C 6 H 4 (CH 3 )] − , the thiophen-2-ylide anion (C 4 H 3 S − ), methylato (MeO − ), ethylato (EtO − ), tert-butylato (tert-BuO − ), MeS − , MeSe − , (tert-Bu)S − , (tert-Bu)Se − , dimethylamido (NMe 2 − ), diethylamido (NEt 2 − ), methylethylamido (NMeEt − ), N-pyrrolidido [NC 4 H 8 ] − , chloride (Cl − ) or bromide (Br − ),
Y is the oxo group [O] 2− or the imido group [NR 6 ] 2− , where R 6 is a cyclic, branched or linear alkyl having up to 6 C atoms or is a substituted or unsubstituted aryl having up to 12 C atoms.

4. Metal complex according to claim 1 , wherein
R 1 is hydrogen or a linear or branched alkyl radical having up to 4 carbon atoms,
R 2 is hydrogen or a linear or branched alkyl radical having up to 4 carbon atoms,
R 3 is hydrogen, CH 3 , C 2 H 5 , NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
R 4 and R 5 independently of one another are hydrogen, CH 3 or C 2 H 5 ,
X is the hydride anion (H − ), methylide (CH 3 − ), ethylide (C 2 H 5 − ), the phenylide anion (C 6 H 5 − ), the ortho-, meta-, or para-tolylide anion [C 6 H 4 (CH 3 )] − , methylato (MeO − ), ethylato (EtO − ), MeS − , MeSe − , dimethylamido (NMe 2 − ), diethylamido (NEt 2 − ), methylethylamido (NMeEt − ), chloride (Cl − ) or bromide (Br − ),
Y is the oxo group [O] 2− or the imido group [NR 6 ] 2− , where R 6 is a branched or linear alkyl having up to 5 C atoms or is a substituted or unsubstituted aryl having up to 8 C atoms.

5. Metal complex according to claim 1 , wherein
R 1 is hydrogen or a linear or branched alkyl radical having up to 3 carbon atoms,
R 2 is hydrogen or a linear or branched alkyl radical having up to 3 carbon atoms,
R 3 is CH 3 , C 2 H 5 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
R 4 and R 5 independently of one another are CH 3 or C 2 H 5 ,
X is the hydride anion (H − ), methylide (CH 3 − ), ethylide (C 2 H 5 − ), the phenylide anion (C 6 H 5 − ), the ortho-, meta-, or para-tolylide anion [C 6 H 4 (CH 3 )] − , methylato (MeO − ), MeS − , dimethylamido (NMe 2 − ), diethylamido (NEt 2 − ) or chloride (Cl − ),
Y is the imido group [NR 6 ] 2− , where R 6 is a linear or branched alkyl having up to 4 C atoms.

6. Metal complex according to claim 1 , wherein
R 1 and R 2 are both, independently of one another, a linear alkyl radical having up to 3 carbon atoms,
R 3 is CH 3 , C 2 H 5 or N(CH 3 ) 2 ,
R 4 and R 5 independently of one another are CH 3 or C 2 H 5 ,
X is a hydride anion (H − ), methylide (CH 3 − ), ethylide (C 2 H 5 − ), isopropylide (iso-C 3 H 7 − ),
Y is the imido group [N t Bu] 2− .

7. Metal complex according to claim 1 , having the formula 2

wherein
M is B, Al, Ga, In, Fe, Zn or Pd,
R 3 is CH 3 or N(CH 3 ) 2 ,
X is the hydride anion (H − ) or methylide (CH 3 − ),
a is 1 or 2 and
n is 0, 1 or 2.

8. Metal complex according to claim 1 , wherein the metal complexes have the following formula 3

wherein
M is B, Al, Ga, In, Zn, Fe or Pd,
X is the hydride anion (H − ) or methylide (CH 3 − ),
a is 1 or 2 and
n is 0, 1 or 2.

9. Metal complex according to claim 8 , wherein the N-aminoguanidinate-ligand is N-dimethylamino-N′,N″-trimethylguanidinate (datg).

10. Metal complex according to claim 8 , wherein M is B, Al, Ga, In or Pd.

11. Metal complex according to claim 1 , wherein the metal complexes have the following formula 4

Assignees

• Umicore Ag & Co Kg

Inventors

• Sundermeyer Joerg
• Schlechter Katrin

Classifications

• C23C16/30

  Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides · CPC title

• C07F5/027

  Organoboranes and organoborohydrides · CPC title

• C07F5/065

  compounds with an Al-H linkage · CPC title

• C07F5/05

  Cyclic compounds having at least one ring containing boron but no carbon in the ring · CPC title

• C07F5/069 Primary

  without C-aluminium linkages · CPC title