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US 6,184,403 B2Granted
MOCVD precursors based on organometalloid ligands
AssigneeThe Research Foundation of State University of New York
InventorsJohn T. Welch, Paul J. Toscano, Rolf Claessen, Andrei Kornilov, Kulbinder Kumar Banger
Life of this patent
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Abstract
Chemical vapor deposition processes utilize as precursors volatile metal complexes with ligands containing metalloid elements silicon, germanium, tin or lead.
Claims42
A compound of formula I:
- wherein
- R1 is C2 or higher alkyl, substituted alkyl, haloalkyl, cycloalkyl, C10 or higher aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, acyl, alkyl carboxylate, aryl carboxylate, alkenyl, alkynyl, or E2(R6)(R7)(R8);
- R2is H, halogen, nitro, or haloalkyl;
- E1 and E2 are independently Si, Ge, Sn, or Pb;
- R3, R4, R5, R6, R7, and R8 are independently chosen from alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, arylalkyl, alkoxy, alkenyl, alkynyl or R4 and R5, or R7 and R8 taken together form a divalent alkyl radical;
- Y and Z are independently O, S or NR9;
- and
- R9 is alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, alkenyl, or alkynyl.
5 more elements
A metal-ligand complex of formula II
- M Ln·pD ((II)
- wherein
- M is a metal chosen from the group consisting of:
- Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, Mo, W, Mn, Re, Sm, Fe, Ru, Eu, Os, Co, Rh, Ir, Gd, Ni, Pd, Pt, Tb, Cu, Ag, Au, Dy, Ho, Al, Ga, In, Tl, Er, Ge, Sn, Pb, Tm, Sb, Bi, Yb, Lu, Th, and U;
- D is a neutral coordinating ligand;
- n is equal to the valence of M;
- p is zero or an integer from 1 to 6;
- and
- L is a ligand of formula III
- wherein
- R1 is alkyl, substituted alkyl, haloalkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, acyl, alkyl carboxylate, aryl carboxylate, alkenyl, alkynyl, or E2(R6)(R7)(R8);
- R2 is H, halogen, nitro, or haloalkyl;
- E1 and E2 are independently Si, Ge, Sn, or Pb;
- R3, R4, R5, R6, R7, and R8 are independently chosen from alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, arylalkyl, alkoxy, alkenyl, alkynyl or R4 and R5, or R7 and R8 taken together form a divalent alkyl radical;
- Y and Z are independently O, S or NR9;
- and
- R9 is alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, alkenyl, or alkynyl.
14 more elements
A process for the preparation of a compound of formula I:
- wherein
- R1 is C2 or higher alkyl, substituted alkyl, haloalkyl, cycloalkyl, C10 or higher aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, acyl, alkyl carboxylate, aryl carboxylate, alkenyl, alkynyl, or E2(R6)(R7)(R8);
- R2 is H, halogen, nitro, or haloalkyl;
- E1 and E2 are independently Si, Ge, Sn, or Pb;
- R3, R4, R5, R6, R7, and R8 are independently chosen from alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, arylalkyl, alkoxy, alkenyl, alkynyl or R4 and R5, or R7 and R8 taken together form a divalent alkyl radical;
- Y and Z are independently O, S or NR9;
- and
- R9 is alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, alkenyl, or alkynyl
- comprising:
- (a) reacting a compound of formula E(R3)(R4)(R5)C(O)CH2R2 with a lithiumdialkylamide to form a lithium enolate anion;
- and
- (b) reacting the anion formed in step (a) with a compound of formula R1C(Y)Q, wherein Q is a leaving group.
9 more elements
A process for the preparation of a compound of formula I
- wherein
- R1 is C2 or higher alkyl, substituted alkyl, haloalkyl, cycloalkyl, C10 or higher aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, acyl, alkyl carboxylate, aryl carboxylate, alkenyl, alkynyl, or E2(R6)(R7)(R8);
- R2 is H, halogen, nitro, or haloalkyl;
- E1 and E2 are independently Si, Ge, Sn, or Pb;
- R3, R4, R5, R6, R7, and R8 are independently chosen from alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, arylalkyl, alkoxy, alkenyl, alkynyl or R4 and R5, or R7 and R8 taken together form a divalent alkyl radical;
- Y is O, S or NR9;
- Z is O;
- and
- R9 is alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, alkenyl, or alkynyl;
- comprising:
- (a) reacting an alkyllithium compound, a 1,3-dithiane of formula
- and a copper salt to form a lithium 1,3-dithianylcuprate;
- (b) reacting the lithium 1,3-dithianylcuprate formed in step (a) with a compound of formula R1C(Y)CHR2 Br;
- and
- (c) deprotecting by treatment with a mercury reagent.
12 more elements
A process for the preparation of a metal-ligand complex of formula II
- M Ln·pD (II)
- wherein
- M is a metal chosen from the group consisting of:
- Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, Mo, W, Mn, Re, Sm, Fe, Ru, Eu, Os, Co, Rh, Ir, Gd, Ni, Pd, Pt, Th, Cu, Ag, Au, Dy, Ho, Al, Ga, In, Tl, Er, Ge, Sn, Pb, Tm, Sb, Bi, Yb, Lu, Th and U;
- D is a neutral coordinating ligand;
- n is equal to the valence of M;
- p is zero or an integer from 1 to 6;
- and
- L is a ligand of formula III:
- wherein
- R1 is alkyl, substituted alkyl, haloalkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, acyl, alkyl carboxylate, aryl carboxylate, alkenyl, alkynyl, or E2(R6)(R7)(R8);
- R2 is H, halogen, nitro, or haloalkyl;
- E1 and E2 are independently Si, Ge, Sn, or Pb;
- R3, R4, R5, R6, R7, and R8 are independently chosen from alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, arylalkyl, alkoxy, alkenyl, alkynyl or R4 and R5, or R7 and R8 taken together form a divalent alkyl radical;
- Y and Z are independently O, S or NR9;
- and
- R9 is alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylallyl, alkoxy, alkenyl, or alkynyl;
- comprising:
- (a) reacting a compound of formula E(R3)(R4 )(R5)C(O)CH2R2 with a lithiumdialkylamide to form a lithium enolate anion;
- (b) reacting the anion formed in step (a) with a compound of formula R1C(Y)Q, wherein Q is a leaving group;
- (c) forming an anion of the ligand;
- and
- (d) reacting the anion formed in step (c) with a metal salt of formula MA, where A is a suitable anion, to form the metal-ligand complex.
20 more elements
A process for the preparation of a metal-ligand complex of formula II
- MLn·pD (II)
- wherein
- M is a metal chosen from the group consisting of:
- Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, Mo, W, Mn, Re, Sm, Fe, Ru, Eu, Os, Co, Rh, Ir, Gd, Ni, Pd, Pt, Th, Cu, Ag, Au, Dy, Ho, Al, Ga, In, Tl, Er, Ge, Sn, Pb, Tm, Sb, Bi, Yb, Lu, Th and U;
- D is a neutral coordinating ligand;
- n is equal to the valence of M;
- p is zero or an integer from 1 to 6;
- and
- L is a ligand of formula III
- wherein
- R1 is alkyl, substituted alkyl, haloalkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, acyl, alkyl carboxylate, aryl carboxylate, alkenyl, alkynyl, or E2(R6)(R7)(R8);
- R2 is H, halogen, nitro, or haloalkyl;
- E1 and E2 are independently Si, Ge, Sn, or Pb;
- R3, R4, R5, R6, R7, and R8 are independently chosen from alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, arylalkyl, alkoxy, alkenyl, alkynyl or R4 and R5, or R7 and R8 taken together form a divalent alkyl radical;
- Y and Z are independently O, S or NR9;
- and
- R9 is alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, alkenyl, or alkynyl;
- comprising:
- (a) reacting an alkyllithium compound, a 1,3-dithiane of formula
- and a copper salt to form a lithium 1,3-dithianylcuprate;
- (b) reacting the lithium 1,3-dithianylcuprate formed in step (a) with a compound of formula R1C(Y)CHR2 Br;
- and
- (c) deprotecting by treatment with a mercury reagent to form a ligand;
- (d) forming an anion of the ligand;
- and
- (e) reacting the anion formed in step (c) with a metal salt of formula MA, where A is a suitable anion, to form the metal-ligand complex.
23 more elements
A process for the preparation of a metal-ligand complex of formula II
- MLn·pD (II)
- wherein
- M is a metal chosen from the group consisting of:
- Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, Mo, W, Mn, Re, Sm, Fe, Ru, Eu, Os, Co, Rh, Ir, Gd, Ni, Pd, Pt, Th, Cu, Ag, Au, Dy, Ho, Al, Ga, In, Tl, Er, Ge, Sn, Pb, Tm, Sb, Bi, Yb, Lu, Th, and U;
- D is a neutral coordinating ligand;
- n is equal to the valence of M;
- p is zero or an integer from 1 to 6;
- and
- L is a ligand of formula III:
- wherein
- R1 is alkyl, substituted alkyl, haloalkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, acyl, alkyl carboxylate, aryl carboxylate, alkenyl, alkynyl, or E2(R6)(R7)(R8);
- R2is H, halogen, nitro, or haloalkyl;
- E1 and E2 are independently Si, Ge, Sn, or Pb;
- R3, R4, R5, R6, R7, and R8 are independently chosen from alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, arylalkyl, alkoxy, alkenyl, alkynyl or R4 and R5, or R7 and R8 taken together form a divalent alkyl radical;
- Y and Z are independently O, S or NR9;
- and
- R9 is alkyl, substituted alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, arylalkyl, alkoxy, alkenyl, or alkynyl;
- comprising:
- (a) reacting a compound of formula E1R3R4R5Li with a compound of formula R1C(Y)CHR2 OR, where R is alkyl or phenyl;
- and
- (b) reacting the compound formed in step (a) with a metal salt of formula MA, where A is a suitable anion, to form the metal-ligand complex.
18 more elements
Dependencies are inferred from the claim text.