Abstract: A carbonylation process for the preparation of carboxylic acid esters is described wherein carbon monoxide is contacted with at least one alcohol in the presence of a catalyst system having the general formula:B.sub.x Me[Me'(CO).sub.a (L).sub.b ].sub.2and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 1 to about 16, wherein B is a Lewis base capable of coordinating with a Group IIA metal; Me is a Group IIA metal, preferably magnesium, Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB and VIII of the Periodic Table of the Elements; L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with the transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. A typical preferred catalyst system is represented by the general formula: (C.sub.4 H.sub.8 O).

Abstract: A method is described for the preparation of high surface area metal fluorides and metal oxyfluorides comprising reacting high surface area metal oxides with a fluorocarbon vapor wherein the fluorocarbon is selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1 to 3 and totally or partially fluorinated C.sub.2 -C.sub.6 alkanes, alkenes and alkynes and C.sub.5 -C.sub.6 cyclic alkanes, preferably fluoroform (CHF.sub.3) wherein the metal oxides and the fluorocarbon vapors are contacted at a temperature of from about 300.degree. to about 800.degree. C., for a time sufficient to effect the essentially complete conversion of the metal oxides into metal fluorides or the partial conversion of the metal oxides into metal oxyfluorides.

Abstract: A carbonylation process for the preparation of carboxylic acid esters is described wherein carbon monoxide is contacted with at least one alcohol in the presence of a catalyst system having the general formula:B.sub.x Me[Me'(CO).sub.a (L).sub.b ].sub.2and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 1 to about 16, wherein B is a Lewis base capable of coordinating with a Group IIA metal; Me is a Group IIA metal, preferably magnesium, Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB and VIII of the Periodic Table of the Elements; L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with the transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. A typical preferred catalyst system is represented by the general formula: (C.sub.4 H.sub.8 O).

Abstract: A carbonylation catalyst composition comprising a mixture of:(a) (C.sub.4 H.sub.8 O).sub.4 Mg[Co(CO).sub.3 P(C.sub.4 H.sub.9).sub.3 ].sub.2 or (C.sub.4 H.sub.8 O).sub.4 Mg[Rh(CO).sub.3 P(C.sub.4 H.sub.9).sub.3 ].sub.2 and an organo iodine compound selected from the group consisting of CH.sub.3 I, CH.sub.2 CH.sub.3 I, and C.sub.6 H.sub.5 I.

Abstract: New heteronuclear noble metal cluster complexes have been discovered and synthesized for the first time. These complexes are (pyridine).sub.2 Pt[Ir.sub.6 (CO).sub.15 ], (pyridine).sub.2 -Pt[Ir.sub.2 (CO).sub.7 ], (pyridine).sub.3 Pt[Ru.sub.3 (CO).sub.12 ], ((C.sub.6 H.sub.5).sub.3 P).sub.2 -Pt[Ir(CO).sub.3 P (C.sub.6 H.sub.5).sub.3 ].sub.2, ((C.sub.6 H.sub.5).sub.3 P).sub.2 Rh(CO)[Ir(CO).sub.4 ], and (pyridine).sub.2 Pt[Rh(CO).sub.2 (P(C.sub.6 H.sub.5).sub.3).sub.2 ].sub.2.These new heteronuclear noble metal cluster complexes are useful as supported mixed noble metal catalyst precursors. These new cluster complexes, of known stoichiometry, are deposited on anhydrous refractory inorganic oxide or carbon supports and then reduced resulting in the formation of a supported heteronuclear noble metal catalyst having the same metals stoichiometry as the starting cluster complexes.

Abstract: A method is described for the preparation of high surface area metal fluorides and metal oxyfluorides comprising reacting high surface area metal oxides with a fluorocarbon vapor wherein the fluorocarbon is selected from the group consisting of CH.sub.4-Q F.sub.Q wherein Q is 1 to 3 and totally or partially fluorinated C.sub.2 -C.sub.6 alkanes, alkenes and alkynes and C.sub.5 -C.sub.6 cyclic alkanes, preferably fluoroform (CHF.sub.3) wherein the metal oxides and the fluorocarbon vapors are contacted at a temperature of from about 300.degree. to about 800.degree. C., for a time sufficient to effect the essentially complete conversion of the metal oxides into metal fluorides or the partial conversion of the metal oxides into metal oxyfluorides.

Abstract: New heteronuclear noble metal cluster complexes have been discovered and synthesized for the first time. These complexes are (pyridine).sub.2 Pt[Ir.sub.6 (CO).sub.15 ], (pyridine).sub.2 Pt[Ir.sub.2 (CO).sub.7 ], (pyridine).sub.3 Pt[Ru.sub.3 (CO).sub.12 ], ((C.sub.6 H.sub.5).sub.3 P).sub.2 Pt[Ir(CO).sub.3 P (C.sub.6 H.sub.5).sub.3 ].sub.2, ((C.sub.6 H.sub.5).sub.3 P).sub.2 Rh(CO)[Ir(CO).sub.4 ], and (pyridine).sub.2 Pt[Rh(CO).sub.2 (P(C.sub.6 H.sub.5).sub.3).sub.2 ].sub.2.These new heteronuclear noble metal cluster complexes are useful as supported mixed noble metal catalyst precursors. These new cluster complexes, of known stoichiometry, are deposited on anhydrous refractory inorganic oxide or carbon supports and then reduced resulting in the formation of a supported heteronuclear noble metal catalyst having the same metals stoichiometry as the starting cluster complexes. In this way, precise control can be exercised over the ratio and distribution of multiple metal components in a mixed noble metal catalyst.

Abstract: A carbonylation process for the preparation of carboxylic acid esters is described wherein carbon monoxide is contacted with at least one alcohol in the presence of a catalyst system having the general formula:B.sub.x Me[Me'(CO).sub.a (L).sub.b ].sub.2and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 1 to about 16, wherein B is a Lewis base capable of coordinating with a Group IIA metal; Me is a Group IIA metal, preferably magnesium, Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB and VIII of the Periodic Table of the Elements; L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with the transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. A typical preferred catalyst system is represented by the general formula: (C.sub.4 H.sub.8 O).

Abstract: New heteronuclear noble metal cluster complexes have been discovered and synthesized for the first time. These complexes are (pyridine).sub.2 Pt[Ir.sub.6 (CO).sub.15 ], (pyridine).sub.2 --Pt[Ir.sub.2 (CO).sub.7 ], (pyridine).sub.3 Pt[Ru.sub.3 (CO).sub.12 ], ((C.sub.6 H.sub.5).sub.3 P).sub.2 --Pt[Ir(CO).sub.3 P(C.sub.6 H.sub.5).sub.3 ].sub.2, ((C.sub.6 H.sub.5).sub.3 P).sub.2 Rh(CO)[Ir(CO).sub.4 ], and (pyridine).sub.2 Pt[Rh(CO).sub.2 (P(C.sub.6 H.sub.5).sub.3).sub.2 ].sub.2.These new heteronuclear noble metal cluster complexes are useful as supported mixed noble metal catalyst precursors. These new cluster complexes, of known stoichiometry, are deposited on anhydrous refractory inorganic oxide or carbon supports and then reduced resulting in the formation of a supported heteronuclear noble metal catalyst having the same metals stoichiometry as the starting cluster complexes.

Abstract: This invention relates to unique supported potassium (or rubidium) - Group VIII-metal cluster catalysts which are useful in CO/H.sub.2 reactions (Fischer-Tropsch synthesis reactions). The novel catalysts of the instant invention are prepared by depositing well characterized potassium (or rubidium) - Group VIII-metal carbonyl cluster complexes onto high surface area supports. Following a subsequent reduction, the precursor bimetallic cluster complexes are decomposed on the support surface forming a potassium (or rubidium) promoted Group VIII-metal cluster catalyst in which the potassium (or rubidium) and Group VIII metals are intimately associated. These unique, highly promoted cluster catalysts have been found to demonstrate high Group VIII-metal dispersions and enhanced Fischer-Tropsch activities and selectivities for producing olefinic and paraffinic hydrocarbons.

Abstract: Hydrocarbon conversion processes wherein hydrocarbon feedstreams are contacted with heteronuclear noble metal catalysts are improved by the use of supported heteronuclear noble metal cluster catalysts prepared from novel supported heteronuclear noble metal cluster complexes. The heteronuclear noble metal cluster complexes used as catalyst precursors are selected from the group consisting of(pyridine).sub.2 Pt[Ir.sub.6 (CO).sub.15 ],(pyridine).sub.2 Pt[Ir.sub.2 (CO).sub.7 ],((C.sub.6 H.sub.5).sub.3 P).sub.2 Pt[IR(CO).sub.3 P(C.sub.6 H.sub.5).sub.3 ].sub.2,(pyridine).sub.2 Pt[Ru.sub.3 (CO).sub.12 ]((C.sub.6 H.sub.5).sub.3 P).sub.2 Rh(CO)[Ir(CO).sub.4 ],(pyridine).sub.2 Pt[Rh(CO).sub.2 (P(C.sub.6 H.sub.5).sub.3).sub.2 ].sub.2.

Abstract: This invention relates to unique supported potassium (or rubidium)-Group VIII-metal cluster catalysts which are useful in CO/H.sub.2 reactions (Fischer-Tropsch synthesis reactions). The novel catalysts of the instant invention are prepared by depositing well characterized potassium (or rubidium)-Group VIII-metal carbonyl cluster complexes onto high surface area supports. Following a subsequent reduction, the precursor bimetallic cluster complexes are decomposed on the support surface forming a potassium (or rubidium) promoted Group VIII-metal cluster catalyst in which the potassium (or rubidium) and Group VIII metals are intimately associated. These unique, highly promoted cluster catalysts have been found to demonstrate high Group VIII-metal dispersions and enhanced Fischer-Tropsch activities and selectivities for producing olefinic and paraffinic hydrocarbons.

Abstract: The instant invention relates to a novel catalyst which comprises a physical mixture of (1) at least one catalytically active transition metal selected from Group VIII of the Periodic Table of the Elements in combination with at least one alkaline earth metal oxide, and (2) an acidic refractory oxide. The combination of one or more of said Group VIII metals and one or more alkaline earth metal oxides may be provided by supporting said metals and said oxides on a nonacidic refractory oxide support. These catalysts are useful in hydrocarbon conversion processes and are characterized as having improved stability under oxidizing conditions, for example, the high temperature oxidation treatments encountered in regenerating deactivated reforming catalysts.

Abstract: A process for the preparation of ethers is described wherein at least one alcohol is contacted in the presence of carbon monoxide with a catalyst system having the general formula:B.sub.x Me[Me'(CO).sub.a (L).sub.b ].sub.2and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 16 to about 100 wherein B is a Lewis base capable of coordinating with a Group IIA metal; Me is a Group IIA metal, preferably magnesium; Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB and VIII of the Periodic Table of the Elements; L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with the transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. A typical preferred catalyst system is represented by the general formula:(C.sub.4 H.sub.8 O).sub.4 Mg[Mn(CO).sub.4 P(C.sub.

Abstract: The instant invention relates to a novel catalyst which comprises a physical mixture of (1) at least one catalytically active transition metal selected from Group VIII of the Periodic Table of the Elements in combination with at least one alkaline earth metal oxide, and (2) an acidic refractory oxide. The combination of one or more of said Group VIII metals and one or more alkaline earth metal oxides may be provided by supporting said metals and said oxides on a nonacidic refractory oxide support. These catalysts are useful in hydrocarbon conversion processes and are characterized as having improved stability under oxidizing conditions, for example, the high temperature oxidation treatments encountered in regenerating deactivated reforming catalysts.

Abstract: The instant invention relates to high surface area multilayered oxide supports coated with ruthenium of the type Ru-MgO-MgAl.sub.2 O.sub.4 -MgAl.sub.2 O.sub.4 +Mg.sub.2 SiO.sub.4 -Core. The system comprises ruthenium on a critical amount of free MgO, i.e., at least 2 wt. % minimum, on pre-reacted Al.sub.2 O.sub.3 which itself is on a monolithic ceramic substrate. This combination demonstrates the desirable, and previously unachievable characteristic of resistance to ruthenium volatilization and agglomeration, coupled with high catalytic activity. The high surface area oxides (MgO+Al.sub.2 O.sub.3) are strongly bonded to and reacted with the monolithic core substructure so as to possess physical strength.

Abstract: This invention relates to the treatment of Group VIII, noble metal, catalysts, wherein said noble metal is present on a refractory support and where said noble metal exists as large agglomerated crystallites, e.g., greater than 50 A, which comprises contacting said catalyst with fluorine at a temperature and for a time sufficient to disperse said crystallites to crystallites having substantially smaller particle size. The noble metals which may be dispersed by this process include Pt, Pd, Ru, Ir and Rh. This invention is especially suitable for redispersing iridium-containing catalysts.

Abstract: The preparation of novel compounds of the general formula B.sub.x Me(M).sub.2 is described; wherein B is a Lewis base, x is an integer 1 through 4, Me is a Group IIA metal, and M is a transition metal carbonyl or a substituted transition metal carbonyl group. These compounds are shown to have utility as catalysts for hydrogenation, butadiene oligomerization, carbonylation, isomerization and hydroformylation. In a preferred embodiment the tetrakis tetrahydrofuran adduct of the magnesium-cobalt phosphine substituted carbonyl complex is shown to effectively catalyze the hydroformylation of 1-hexene.

Abstract: A process for preparing oxygenated products comprising aldehydes, which have high normal to branched-chain isomer ratios. The process involves using particularly characterized rhodium-containing complex catalysts under a specific combination of carefully controlled reaction conditions. The product aldehydes as made above may be condensed and hydrogenated to form saturated aldehyde dimers thereof.

Abstract: A process for preparing oxygenated products comprising aldehydes, which have high normal to branched-chain isomer ratios. The process involves using particularly characterized rhodium-containing complex catalysts under a specific combination of carefully controlled reaction conditions. The product aldehydes as made above may be condensed and hydrogenated to form saturated aldehyde dimers thereof.