Metal complexes with N-Aminoamidinate ligands

Patent metadata

Field	Value
Publication number	US-9353139-B2
Application number	US-201214000962-A
Country	US
Kind code	B2
Filing date	Feb 20, 2012
Priority date	Feb 25, 2011
Publication date	May 31, 2016
Grant date	May 31, 2016

Abstract

The invention relates to new metal complexes having N-aminoamidinate ligands, more particularly metal complexes having N,N′-bis(dimethylamino)acetamidinate, N,N′-bis(dimethylamino)formamidinate, N-dimethylaminoacetamidinate or N-dimethylamino-N′-isopropyl-acetamidinate ligands as well as to their preparation and use. The metal complexes are characterized by a five-membered chelate ring. The metal complexes are formed with the metals from the main groups of the PTE, but also with transition-group elements such as tantalum (Ta), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) or zinc (Zn), and also with precious metals such as palladium (Pd).
The complexes of the invention find use as precursors for the preparation of functional layers by means of gas-phase thin-film processes such as CVD, MO-CVD and ALD. Additionally they may be used as catalysts for olefin hydroamination and for olefin polymerization.

First claim

The invention claimed is:

1. A metal complex having at least one N-aminoamidinate ligand, wherein the metal complex is constructed according to general formula 1

wherein
M is a metal selected from groups 1 to 15 of the Periodic Table of the Elements (PTE),
R 1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 8 C atoms, or a substituted or unsubstituted aryl radical having up to 20 C atoms,
R 2 and R 3 independently of one another are hydrogen, CH 3 or C 2 H 5 ,
R 4 is hydrogen, CH 3 , NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
X is a monoanionic co-ligand selected from the group consisting of the hydride anion (H − ), the group of the halides, the group of the cyclic, linear or branched alkylide radicals having up to 8 C atoms, the group of substituted or unsubstituted arylide and heteroarylide radicals having up to 10 C atoms, the group of alkoxylato ligands, from the group of alkylthiolato or alkylselenato ligands, andthe group of secondary amido ligands,
Y is a dianionic coligand selected from the group consisting of the oxo group [O] 2− and the imido group [NR 5 ] 2− , where R 5 is a cyclic, branched or linear alkyl radical having up to 8 C atoms or is a substituted or unsubstituted aryl radical having up to 20 C atoms,
L is a neutral 2-electron donor ligand, wherein if M is scandium, L is not a pentamethylcyclopentadiene (Cp*) 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. The metal complex according to claim 1 , wherein
R 1 is CH 3 , C 2 H 5 , C 6 H 5 , tolyl, 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl (mesityl),
R 2 and R 3 independently of one another are hydrogen, CH 3 or C 2 H 5 ,
R 4 is hydrogen, CH 3 , NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
X is 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 − ) or N-pyrrolidido [NC 4 H 8 ] − , and
Y is the imido group [N t Bu] 2− .

3. The metal complex according to claim 1 , wherein the radical X is a hydride anion (H − ), chloride (Cl − ), bromide (Br − ), methylide (CH 3 − ), ethylide (C 2 H 5 − ), dimethylamide (NMe 2 − ) or diethylamide (NEt 2 − ).

4. The metal complex according to claim 1 , wherein L is pyridine, dioxane, NH 3 , THF, CO, an alkylphosphine, or an arylphosphine.

5. The metal complex according to claim 1 , wherein the complex comprises a five-membered chelate ring.

6. The metal complex according to claim 1 , wherein M is selected from the group consisting of aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), arsenic (As) and antimony (Sb), titanium (Ti), zirconium (Zr), hafnium (Hf), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn).

7. The metal complex according to claim 1 , wherein M is selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt).

8. The metal complex according to claim 1 , wherein at least one of the ligands is an N-aminoamidinate ligand selected from the group consisting of N,N′-bis(dimethylamino)acetamidinate (“bdma”), N-mono(dimethylamino)acetamidinate (“dama”), mono(dimethylamino)acetamidinate (“mdma”) and N,N′-bis(dimethylamino)formamidinate (“bdmf”).

9. The metal complex according to claim 8 , wherein at least one of the N-aminoamidinate ligands is an N,N′-bis(dimethylamino)acetamidinate (“bdma”).

10. The metal complex according to claim 1 , wherein the complex comprises a dimeric structure with bridging ligand functions X, Y or L.

11. A metal complex having at least one neutral N-aminoamidine ligand, wherein the metal complex is constructed according to general formula 2

wherein
M is a transition metal selected from group 1 or 11 of the Periodic Table of the Elements (PTE),
R 1 is hydrogen or a cyclic, linear or branched alkyl radical having up to 8 C atoms, or a substituted or unsubstituted aryl radical having up to 20 C atoms,
R 2 and R 3 independently of one another are hydrogen, CH 3 or C 2 H 5 ,
R 4 is hydrogen, CH 3 , NH 2 , N(CH 3 ) 2 or N(C 2 H 5 ) 2 ,
X is a monoanionic coligand selected from the group consisting of the hydride anion (H − ), the group of halides, the group of cyclic, linear or branched alkylide radicals with up to 8 C atoms, the group of substituted or unsubstituted arylide and heteroarylide radicals with up to 10 C atoms, the group of alkoxylato ligands, the group of alkylthiolato or alkylselenato ligands, and the group of secondary amido ligands,
Y is a dianionic co-ligand selected from the group consisting of the oxo group [O] 2− , and the imido group [NR 5 ] 2− , wherein R 5 is a cyclic, branched or linear alkyl radical with up to 8 C atoms or is a substituted or unsubstituted aryl radical with up to 20 C atoms,
L is a neutral 2-electron donor ligand, wherein the neutral N-aminoamidine ligand is N, N′-bis(dimethylamino)acetamidine (“H-bdma”),
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.

12. A metal complex having N-aminoamidinate ligands in accordance with formula 4,

wherein the monoanionic N-aminoamidinate ligands of index c and the neutral N-aminoamidino ligands of index b are combined in one complex and on one coordination centre,
and wherein the indices b and c independently of one another represent the integers 1, 2 or 3 and wherein
M is a metal selected from groups 1 to 15 of the Periodic Table of the Elements (PTE),
X is a monoanionic co-ligand selected from the group consisting of the hydride anion (H − ), the group of the halides, the group of the cyclic, linear or branched alkylide radicals having up to 8 C atoms, the group of substituted or unsubstituted arylide and heteroarylide radicals having up to 10 C atoms, the group of alkoxylato ligands, from the group of alkylthiolato or alkylselenato ligands, andthe group of secondary amido ligands,
Y is a dianionic coligand selected from the group consisting of the oxo group [O] 2− , and the imido group [NR 5 ] 2− , where R 5 is a cyclic, branched or linear alkyl radical having up to 8 C atoms or is a substituted or unsubstituted aryl radical having up to 20 C atoms,
L is a neutral 2-electron donor ligand, and
n, m, and p each independently of one another are 0, 1, 2, 3 or 4.

13. A process for preparing the metal complex according to claim 1 , comprising reacting a suitable metal starting compound with a neutral N-aminoamidine ligand in an organic solvent in an alkane or amine elimination.

14. A process for preparing the metal complex according to claim 1 , comprising using a base to deprotonate the neutral N-aminoamidine ligand and subsequently reacting a suitable metal starting compound with the neutral N-aminoamidine ligand i

Assignees

• Sundermeyer Joerg
• Schorn Wolf
• Karch Ralf
• Umicore Ag & Co Kg

Inventors

• Sundermeyer Joerg
• Schorn Wolf
• Karch Ralf

Classifications

• C07F5/063

  Chemistry & Metallurgy · mapped topic

• C07F5/00

  Compounds containing elements of Groups 3 or 13 of the Periodic Table · CPC title

• C07C257/14

  having carbon atoms of amidino groups bound to acyclic carbon atoms · CPC title

• B01J2531/40

  Complexes comprising metals of Group IV (IVA or IVB) as the central metal · CPC title

• C07F5/069

  without C-aluminium linkages · CPC title