Bridged metal complexes

Details Bridged metal complexes Bridged metal complexes

2001-04-10

2002-12-31

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Chalcogen in the nitrogen containing substituent

C544S225000, C548S103000, C556S007000, C556S027000, C556S053000, C568S006000, C502S103000, C502S117000, C526S161000, C526S943000

Reexamination Certificate

active

06500949

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates to certain bridged Group 4 transition metal complexes possessing an unique bridging structure and to olefin polymerization catalysts obtained from such complexes. In another embodiment the invention relates to an unique process for preparing such metal complexes and intermediate compounds used in such synthesis. More particularly, the unique bridge of the foregoing metal complexes consists of amido-substituted boron atoms characterized in that the amido group contains a ligand containing an element from group 15 or 16 of the Periodic Table of the Elements.
In
Angew. Chem. Int. Ed. Engl.,
36, 21, p2338-2340 (1997) and in
Phosphorus Sulfur, and Silicon,
124 & 125, p561-565 (1997) amido substituted boron bridged ferrocenophanes useful for forming poly(ferrocenes) by a ring opening polymerization were disclosed. The synthesis and characterization of Group 1 and 2 metal and tin complexes of 1,2-bis(dimethylamino)-1,2-di-9-fluorenyldiboranes were disclosed in
Chem. Ber.,
127, p1901-1908, (1994). Diboranes having structure similar to those employed in the foregoing study were disclosed by the same researchers in
Eur. J. Inorg. Chem., p
505-509 (1998). Ferrocenophane derivatives of similar bisboranes for further molecular property studies were disclosed by
J. Organomet. Chem.,
530 p117-120 (1997). In
Organometallics,
16, p4546-4550 (1997) boron bridged ansa metallocene complexes including dimethylsulfide and phosphine adducts thereof of possible use in Ziegler-Natta-type olefin polymerizations were disclosed.
In the patent literature, bridged metal complexes for use as olefin polymerization catalyst components, including such complexes containing one or more boron atoms in the bridge are generically disclosed by EP-A-416,815 and WO 98/39369. Certain techniques for preparing boron bridged metallocenes, including the use of deprotonating agents that are weakly nucleophilic bases are disclosed in U.S. Pat. No. 5,962,718.
SUMMARY OF THE INVENTION
The present invention relates to an improved process for forming certain bridged Group 4 transition metal complexes corresponding to the formula:
wherein:
M is a Group 4 metal, preferably zirconium, said metal M being in the +2, +3 or +4 formal oxidation state;
Y
1
and Y
2
are independently anionic, cyclic or non-cyclic, &pgr;-bonded groups,
Q, independently each occurrence, is a neutral, anionic or dianionic ligand group, said Q having up to 50 atoms not counting hydrogen;
j is an integer from 1 to 4, selected with respect to the oxidation state of M and the electronic nature of Q to provide overall charge balance to the compound;
R
1
is independently each occurrence hydrogen, a hydrocarbyl group, a tri(hydrocarbyl)silyl group, or a tri(hydrocarbyl)silylhydrocarbyl group, or one of the foregoing multiatomic groups further substituted with one or more di(hydrocarbyl)amino- or hydrocarbyloxy- groups, said R
1
group containing up to 50 atoms not counting hydrogen, and optionally both R
1
groups may be joined together, optionally by means of one or more divalent bridging groups derived from the foregoing di(hydrocarbyl)amino- or hydrocarbyloxy- substituent groups, thereby forming a dianionic ligand group,
the steps of the process comprising:
(1) contacting a boron trihalide with a magnesium dianionic salt corresponding to the formula Mg(Y
1
H)(Y
2
H), wherein Y
1
and Y
2
are as previously defined to prepare a metal complex according to the formula:
wherein X is halide;
(2) aminating the boron bridging atom thereby forming a compound of Formula 3,
wherein R
1
is as previously defined,
(3) deprotonating the product of step (2) of Formula 3 by contact with a deprotonating agent; especially a weak nucleophilic base, and
(4) contacting the product of step (3) with a transition metal salt of the formula MY
3
y
(LB)
b
, wherein
M is as previously defined;
Y
3
is Q or a leaving group, especially halide, more especially bromide or chloride;
y is an integer from 0 to 4 selected to provide charge balance in the transition metal salt;
LB is a Lewis base compound; and
b is an integer from 0 to 3.
According to the present invention there is also provided a process for forming a compound corresponding to the formula:
wherein X is halide, preferably bromide or chloride; and
Y
1
and Y
2
are independently anionic, cyclic or non-cyclic, &pgr;-bonded groups, the steps of the process comprising:
(1) contacting a boron trihalide with a magnesium dianionic salt corresponding to the formula Mg(Y
1
H)(Y
2
H), wherein Y
1
and Y
2
are as previously defined under reaction conditions to thereby prepare the metal complex of formula 2.
In a final embodiment, the present invention relates to certain novel bridged Group 4 transition metal complexes corresponding to the formula:
wherein:
M is a Group 4 metal, preferably zirconium, said metal M being in the +2, +3 or +4 formal oxidation state;
Y
1
and Y
2
are independently anionic, cyclic or non-cyclic, &pgr;-bonded groups,
Q is a neutral, anionic or dianionic ligand group depending on the oxidation state of M, said Q having up to 50 atoms not counting hydrogen;
j is an integer from 1 to 4, selected with respect to the oxidation state of M and the electronic nature of Q to provide overall charge balance to the compound; and
R
1
is independently each occurrence is a substituted hydrocarbyl group, a substituted tri(hydrocarbyl)silyl group, or a substituted tri(hydrocarbyl)silylhydrocarbyl group, said group being substituted with one or more di(hydrocarbyl)amino- or hydrocarbyloxy- groups and containing up to 50 atoms not counting hydrogen, and optionally both R
1
groups may be joined together, optionally by means of one or more divalent bridging groups derived from the foregoing di(hydrocarbyl)amino- or hydrocarbyloxy- substituent groups, thereby forming a dianionic ligand group.
The metal complexes according to Formula 1 or Formula 1′, are usefully employed as components of olefin polymerization catalyst compositions.
DETAILED DESCRIPTION
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1997. Also, any references to a Group or Groups shall be to the Groups or Groups reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. Where any reference is made herein to any publication, patent application or provisional patent application, the contents thereof are incorporated herein in its entirety by reference. By the term “X-bonded” as used herein is meant that bonding occurs through an interaction involving delocalized electrons. By the term, “leaving group” is meant a ligand that is readily displaced by another ligand under ligand exchange conditions.
Suitable Lewis base compounds, LB, in the foregoing reagents and products, include neutral Q groups, especially conjugated dienes, especially 1,4-diphenyl-1,3-butadiene, which are capable of donating an electron pair originating from delocalized &pgr;-electrons contained therein.
All of the foregoing process steps are desirably conducted in an inert solvent, especially an aliphatic or aromatic hydrocarbon or ether, employing temperatures from −100° C. to 150° C. Amination of the boron bridging atom (step (2)) may be accomplished by the use of either an alkali metal amide- or Grignard amide- reagent of the formula MeNR
1
2
, wherein Me is an alkali metal cation or Grignard cation (MgBr
+
or MgCl
+
) (step 2a), or a secondary amine of the formula HNR
1
2
, preferably in excess, (or a mixture of the foregoing secondary amine reagent and a tertiary amine of the formula, NR
3
3
), wherein R
1
is as previously defined and R
3
is R
1
or C
1-4
alkyl (step 2b). By performing the amination after addition of the cyclopentadienyl ligands to the boron bridging group instead of before such addition, the desired product is formed in higher yield and purity. Moreover, use of the foregoing neutral amination conditions of step 2b

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