Brookhaven Science Associates, Lcc

Other

The United States of America As Represented by the United States

R Morris Bullock

Elisabeth Muriel Hauptman

Paul Joseph Fagan

Marcel Schlaf

Vladimir K Dioumaev

Mark Voges

Barbara F M Kimmich

Organometallic complexes are provided, which include a catalyst containing a transition metal, a ligand and a component having the formula GAr. Aris an aromatic ring system selected from phenyl, naphthalenyl, anthracenyl, fluorenyl, or indenyl. The aromatic ring system has at least a substituent selected from fluorine, hydrogen, hydrocarbyl or fluorinated hydrocarbyl, G is substituted or unsubstituted (CH)or (CF), wherein n is from 1 to 30, wherein further one or more CHor CFgroups are optionally replaced by NR, PR, SiR, BR, O or S, or R is hydrocarbyl or substituted hydrocarbyl, GArbeing covalently bonded to either said transition metal or said ligand of said catalyst, thereby rendering said cationic organometallic complex liquid. The catalyst of the organometallic complex can be [CpM(CO)(NHC)L]A, wherein M is an atom of molybdenum or tungsten, Cp is substituted or unsubstituted cyclopentadienyl radical represented by the formula [CQQQQQ], wherein Qto Qare independently selected from the group consisting of H radical, GArChydrocarbyl radical, substituted hydrocarbyl radical, substituted hydrocarbyl radical substituted by GAr, halogen radical, halogen-substituted hydrocarbyl radical, &#x2014;OR, &#x2014;C(O)R', &#x2014;COR&#x2032;, &#x2014;SiR&#x2032;and &#x2014;NR&#x2032;R&#x2033;, wherein R&#x2032; and R&#x2033; are independently selected from the group consisting of H radical, Chydrocarbyl radical, halogen radical, and halogen-substituted hydrocarbyl radical, wherein said Qto Qradicals are optionally linked to each other to form a stable bridging group, NHC is any N-heterocyclic carbene ligand, L is either any neutral electron donor ligand, wherein k is a number from 0 to 1 or L is an anionic ligand wherein k is 2, and Ais an anion. Processes using the organometallic complexes as catalysts in catalytic reactions, such as for example, the hydrosilylation of aldehydes, ketones and esters are also provided.

Recyclable catalysts methods of making and using the same

Catalysts for hydrogenation and hydrosilylation, methods of making and using the same

The present invention is a process for the catalytic hydrogenation of ketones and aldehydes to alcohols at low temperatures and pressures using organometallic molybdenum and tungsten complexes and the catalyst used in the process. The reactants include a functional group which is selected from groups represented by the formulas R*(C&boxH;O)R&prime; and R*(C&boxH;O)H, wherein R* and R&prime; are selected from hydrogen or any alkyl or aryl group. The process includes reacting the organic compound in the presence of hydrogen and a catalyst to form a reaction mixture. The catalyst is prepared by reacting Ph C A with a metal hydride. A represents an anion and can be BF , PF , CF SO or Bar&prime; , wherein Ar&prime;&equals;3,5-bis(trifluoromethyl)phenyl. The metal hydride is represented by the formula: HM(CO) &lsqb;&eegr; :&eegr; &mdash;C H (XH ) PR &rsqb; wherein M represents a molybdenum (Mo) atom or a tungsten (W) atom; X is a carbon atom, a silicon atom or a combination of carbon (C) and silicon (Si) atoms; n is any positive integer; R represents two hydrocarbon groups selected from H, an aryl group and an alkyl group, wherein both R groups can be the same or different. The metal hydride is reacted with Ph C A either before reacting with the organic compound or in the reaction mixture.

Catalytic ionic hydrogenation of ketones using tungsten or molybdenum catalysts with increased lifetimes

Secondary alcohols, specifically diols and polyols, are dehydroxylated to the corresponding primary alcohols using a homogeneous organometallic ruthenium complex catalyst.

Catalytic dehydroxylation of diols and polyols

Ketones and aldehydes are hydrogenated to the corresponding alcohol or alkyl group, using H gas as the stoichiometric reductant, and organometallic ruthenium complexes as the catalysts.

Catalytic reduction of ketones and aldehydes using organometallic ruthenium complexes

The present invention is a process for the catalytic hydrogenation of ketones and aldehydes to alcohols at low temperatures and pressures using organometallic molybdenum and tungsten complexes. The functional group is selected from groups represented by the formulas R(C.dbd.O)R' and R(C.dbd.O)H, wherein R and R' are selected from hydrogen or any alkyl or aryl group. The active catalyst for the process has the form: [CpM(CO).sub.2 (PR*.sub.3) L].sup.+ A.sup.-, where Cp=.eta..sup.5 -R.sup..tangle-solidup..sub.m C.sub.5 H.sub.5-m and R.sup..tangle-solidup. represents an alkyl group or a halogen (F, Cl, Br, I) or R.sup..tangle-solidup. =OR' (where R'=H, an alkyl group or an aryl group) or R.sup..tangle-solidup. =CO.sub.2 R' (where R'=H, an alkyl group or an aryl group) and m=0 to 5; M represents a molybdenum atom or a tungsten atom; R*.sub.3 represents three hydrocarbon groups selected from a cyclohexyl group (C.sub.6 H.sub.11), a methyl group (CH.sub.3), and a phenyl group (C.sub.6 H.sub.5) and all three R* groups can be the same or different or two of the three groups can be the same; L represents a ligand; and A.sup.- represents an anion. In another embodiment, one, two or three of the R* groups can be an OR*.

Catalytic ionic hydrogenation of ketones using tungsten or molybdenum

A process for the non-catalytic hydrogenation of organic compounds, which contain at least one reducible functional group, which comprises reacting the organic compound, a hydride complex, preferably a transition metal hydride complex or an organosilane, and a strong acid in a liquid phase.

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Wading River, NY, United States of America

R Morris Bullock