Catalysts made from transition metal compounds and 4,...

Details Catalysts made from transition metal compounds and 4,... Catalysts made from transition metal compounds and 4,...

1999-06-17

2001-09-18

Hendrickson, Stuart L. (Department: 1754)

Chemistry of inorganic compounds

Carbon or compound thereof

Oxygen containing

C423S655000, C423S659000, C546S023000

Reexamination Certificate

active

06290926

ABSTRACT:

The present invention relates to the preparation of novel catalysts made from transition metal compounds and 4,5-diphosphinoacridine ligands (“acriphos”). The novel ligands employed herein are diphosphine compounds of 4,5-disubstituted acridine of general formula (I) which coordinate transition metals with the two phosphorus atoms and the acridine nitrogen to form transition metal complexes of general formula (II):
The transition metal complexes (II) are novel catalyst systems which can be employed in the catalysis of numerous chemical reactions.
Catalyst systems made from transition metal compounds and phosphine ligands are known in homogeneous catalysis. In the past, a wide variety of monophosphine and “bidentate” diphosphine compounds have been synthesized, and their application in homogeneous catalysis examined [F. R. Hartley and S. Patai (editors),
The Chemistry of Organophosphorus Compounds
, Vol. 1, Wiley, New York, 1990; L. H. Pignolet (editor), Homogeneous
Catalysis with Metal Phosphine Complexes
, Plenum Press, New York, 1983]. Both monophosphine and diphosphine ligands in divalent nickel, palladium and platinum compounds as well as in complex compounds with other transition metals have the disadvantage of becoming oxidized to phosphine oxides in a redox reaction with the transition metal in the presence of water [P. Giannoccaro, E. Panncciulli and G. Vasapallo,
Inorg. Chim. Acta
96 (1985) 179; P. Giannoccaro und G. Vasapallo,
Inorg. Chim. Acta
72 (1983) 51]. In such cases, since the phosphine ligand is irreversibly consumed, the catalysis either is completely brought to a standstill or, in the most favorable case, can be maintained by employing the ligands in a large excess from the beginning or replenishing them in the course of catalysis. Further strengthening of the transition metal-ligand bond can be achieved with “tridentate” triphosphine or “tridentate” diphosphine ligands having a third coordination site with another donor atom, so that their phosphorus centers are less susceptible to chemical changes. However, in contrast to mono- and diphosphines, “tridentate” ligands have found little use for catalysts. In a new review article on polyphosphine ligands [H. A. Mayer and W. C. Kaska,
Chem. Rev.
94 (1994) 1239-1272], the authors have written: “Thus, the idea to use polyphosphine-stabilized metal complexes as catalysts has emerged early. However, the non-dissociative character of the chelating polyphosphines is a disadvantage in catalytic processes which require open sites at the metal center. This seems to limit the application of polyphosphines in catalysis to processes which do not need many available positions at the metal center” (quotation on page 1266).
The “tridentate” ligand 2,6-bis(diphenylphosphinomethyl)pyridine (III, R=Ph) has been known for a long time [W. V. Dahlhoff and S. M. Nelson,
J. Chem. Soc. A
1971, 2184; G. Vasapollo, P. Giannoccaro, C. F. Nobile und A. Sacco,
Inorg. Chim. Acta
48 (1981) 125; A. Sacco, P. Giannoccaro and G. Vasapollo,
Inorg. Chim. Acta
83 (1984) 125; G. Vasapollo, C. F. Nobile and A. Sacco,.
J. Organomet. Chem.
296 (1985) 435; Q. Jiang, D. Van Plew, S. Murtuza, and X. Zhang,
Tetrahedron Lett.
37 (1996) 797]. Ligand (III) has different properties from those of ligands (I) and has some disadvantages with respect to the latter. In addition to metal complexes of structure (IV) with three-coordination in a “T”-shaped planar arrangement similar to that in (II), complexes of structure (V) are also known wherein the diphosphine compounds (III) only serve the function of “bidentate” ligands without an additional metal-nitrogen coordination [P. Giannoccaro, G. Vasapollo and A. Sacco,
J. Chem. Soc. Chem. Commun.
1980, 1136]. One severe drawback of ligand (III) is that basic reagents, such as alcoholates, cleave one of the reactive benzylic hydrogens in transition metal complexes (IV) as a proton, resulting in the formation of “phosphinomethanide” structures (VI) with C—P double bond character. Thus, catalyst systems with (III) as ligands cannot be used in the presence of basic and highly nucleophilic reagents on principle. In addition, ligand (III), being a benzylic phosphine, is extremely sensitive to oxygen [A. Sacco, G. Vasapollo, C. F. Nobile, A. Piergiovanni, M. A. Pellinghelli and M. Lafranchi,.
J. Organomet. Chem.
356 (1988) 397].
Surprisingly, it has now been found that novel transition metal complex compounds (II) prepared from the novel 4,5-diphosphinoacridine ligands (I, “acriphos”) and transition metal compounds of different oxidation stages, wherein R
1
, R
2
, R
3
, R
6
, R
7
, R
8
and R
9
represent hydrogens or, preferably R
9
or R
2
and R
7
, represent one or two alkyl or alkoxy groups each having from 1 to 12 carbon atoms or aryl, NH
2
, NR
2
, NR
3
+
Y
−
(R=C
1
to C
4
alkyl, Y
−
=anions such as halides), OH, COOH, SO
3
H, halogens or CF
3
, or wherein R
1
, R
2
, R
3
, R
6
, R
7
, R
8
and R
9
=H or, preferably R
9
or R
2
and R
7
, represent one or two alkyl, alkoxy or aryl groups substituted with groups such as NH
2
, NR
2
, NR
3
+
Y
−
(R=C
1
to C
4
alkyl, Y
−
=anions such as halides), OH, COOH, SO
3
H, halogens or CF
3
, wherein R
11
, R
12
, R
13
and R
14
are aryl, aralkyl, alkaryl, alkyl or cycloalkyl groups, or phenyl or alkyl groups substituted with groups such as NH
2
, NR
2
, NR
3
+
Y
−
(R=C
1
to C
4
alkyl, Y=anions such as halides), OH, COOH, SO
3
H, halogens or CF
3
, wherein R
11
, R
12
R
13
and R
14
are the same or different, wherein R
11
and R
12
as well as R
13
and R
14
, respectively, may be two alkyl substituents linked to one another to form phosphacycloalkanes, M represents transition metals Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au in different oxidation stages, X represents up to three anions or ligands (n=0, 1, 2, 3), such as halides (F
−
, Cl
−
, Br
−
, I
−
), cyanide, acetate, propionate, trifluoroacetate, acetylacetonate, hexafluoroacetylacetonate, sulfate, alkylsulfonate, arylsulfonate, trifluoromethanesulfonate, hydride, alkyl, aryl, carbon monoxide, nitrosyl, trialkylphosphine, triarylphosphine, trialkylphosphite, triarylphosphite, ethylene, olefins, acetylenes, cyclopentadienyl, benzene, which are bound to the transition metal M, are altogether very active catalysts and thus can be employed for the catalysis of various reactions.
The novel phosphine ligands (I) wherein R
1
, R
2
, R
3
, R
6
, R
7
, R
8
and R
9
represent hydrogens or, preferably R
9
or R
2
and R
7
, represent one or two alkyl or alkoxy groups each having from 1 to 12 carbon atoms or aryl, NH
2
, NR
2
, NR
3
+
Y
−
(R=C
1
to C
4
alkyl, Y
−
=anions such as halides), OH, COOH, SO
3
H, halogens or CF
3
, and wherein R
1
, R
2
, R
3
, R
6
, R
7
, R
8
and R
9
=H or, preferably R
9
or R
2
and R
7
, represent one or two alkyl, alkoxy or aryl groups substituted with groups such as NH
2
, NR
2
, NR
3
+
Y
−
(R=C
1
to C
4
alkyl, Y
−
=anions such as halides), OH, COOH, SO
3
H, halogens or CF
3
, wherein R
11
, R
12
, R
13
and R
14
are aryl, aralkyl, alkaryl, alkyl or cycloalkyl groups, or phenyl or alkyl groups substituted with groups such as NH
2
, NR
2
, NR
3
+
Y
−
(R=C
1
to C
4
alkyl, Y
−
=anions such as halides), OH, COOH, SO
3
H, halogens or CF
3
, wherein R
11
, R
12
, R
13
and R
14
are the same or different, wherein R
11
and R
12
as well as R
13
and R
14
, respectively, are two alkyl substituents bonded to one another to form phosphacycloalkanes, are very tightly coordinated to the metal centers and thus inhibit undesirable reactions at the phosphorus centers which are irreversible under the conditions of catalysis. ligands (I) are distinct from the as yet known diphosphane ligands by a number of properties. The fused, tricyclic, c

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