公开(公告)号：US20150038724A1

公开(公告)日：2015-02-05

申请号：US14461180

申请日：2014-08-15

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Robert H. GRUBBS ,  Matthias SCHOLL

IPC: C07F15/00

CPC classification number: C07F15/0046 ,  B01J31/2273 ,  B01J31/2278 ,  B01J31/2295 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C08G61/08

Abstract: The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are of the formula wherein: M is ruthenium or osmium; X and X1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R1, R6, R7, R8, and R9 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C2-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.

Abstract translation: 本发明涉及具有咪唑烷类配体的新型复分解催化剂及其制备和使用方法。 本发明的催化剂具有下式：其中：M是钌或锇; X和X1各自独立地为阴离子配体; L是中性电子给体配体; 并且，R 1，R 2，R 6，R 7，R 8和R 9各自独立地为氢或选自C 1 -C 20烷基，C 2 -C 20烯基，C 2 -C 20炔基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20链烯氧基，C 2 -C 20炔氧基，芳氧基，C 2 -C 20烷氧基羰基，C 1 -C 20烷基硫醇，芳基硫醇，C 1 -C 20烷基磺酰基和C 2 -C 20烷基亚磺酰基，任选被一个或多个选自 由C 1 -C 10烷基，C 1 -C 10烷氧基，芳基和选自羟基，硫醇，硫醚，酮，醛，酯，醚，胺，亚胺，酰胺，硝基，羧酸的官能团组成的组 ，二硫化物，碳酸酯，异氰酸酯，碳二亚胺，碳烷氧基，氨基甲酸酯和卤素。 已经发现将咪唑烷配体包含在前述的钌或锇催化剂中可显着地改善这些络合物的性质。 本发明的催化剂保持了先前描述的钌络合物的官能团耐受性，同时具有与现有技术的钨和钼体系相比有利的增强的复分解活性。

公开(公告)号：US20140288319A1

公开(公告)日：2014-09-25

申请号：US14055442

申请日：2013-10-16

Applicant: California Institute Of Technology

Inventor： Robert H. GRUBBS ,  Arnab K. CHATTERJEE ,  Tae-Lim CHOI ,  Steven D. GOLDBERG ,  Jennifer A. LOVE ,  John P. MORGAN ,  Daniel P. SANDERS ,  Matthias SCHOLL ,  F. Dean TOSTE ,  Tina M. TRNKA

IPC: C07F9/40 ,  C07F7/18 ,  C07D317/20 ,  C07C29/46 ,  C07C67/297 ,  C07C41/14

CPC classification number: C07F9/40 ,  C07C6/04 ,  C07C17/275 ,  C07C29/40 ,  C07C29/46 ,  C07C41/14 ,  C07C45/69 ,  C07C67/293 ,  C07C67/297 ,  C07C67/343 ,  C07C67/475 ,  C07C201/12 ,  C07C319/20 ,  C07C2531/22 ,  C07C2601/14 ,  C07C2601/16 ,  C07C2603/74 ,  C07D263/14 ,  C07D317/12 ,  C07D317/20 ,  C07D317/24 ,  C07F7/1892 ,  C07F9/4015 ,  C07F15/0046 ,  C07C25/13 ,  C07C47/21 ,  C07C69/007 ,  C07C69/78 ,  C07C69/732 ,  C07C69/56 ,  C07C321/14 ,  C07C69/16 ,  C07C69/533 ,  C07C69/145 ,  C07C69/157 ,  C07C69/18 ,  C07C205/06 ,  C07C33/483

Abstract: The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which may or may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.

Abstract translation: 本发明涉及第8族过渡金属卡宾络合物用作烯烃交叉复分解反应的催化剂。 特别地，用N-杂环卡宾配体取代的钌和锇亚烷基配合物用于催化交叉复分解反应以提供各种取代和官能化的烯烃，包括膦酸酯取代的烯烃，直接卤代烯烃， 三取代烯烃和季烯丙烯烯烃。 本发明还提供了一种使用上述配合物来催化可能或可能不被官能团取代的第一种烯属反应物与多种不同的烯属反应物中的每一种的交叉复分解反应的方法， 或可以不被官能团取代，得到多个结构不同的烯烃产物。 本发明的方法还可用于促进顺式构型中的1,2-二取代烯烃的立体选择性合成。

公开(公告)号：US20230285561A1

公开(公告)日：2023-09-14

申请号：US18187878

申请日：2023-03-22

Applicant: California Institute of Technology ,  The Regents of the University of California

Inventor： Robert H. GRUBBS ,  Marshall L. STOLLER ,  Hoyong CHUNG ,  Alissa M. FITZGERALD ,  Thomas W. KENNY ,  Renee M. THOMAS

IPC: A61K9/107 ,  A61K41/00 ,  A61K47/24 ,  A61K9/08

CPC classification number: A61K9/1075 ,  A61K41/0028 ,  A61K47/24 ,  A61K9/08 ,  A61K2121/00

Abstract: This invention related to manufactured microbubbles, as well as methods of using manufactured microbubbles, for example, in medicinal applications. The invention pertains to the physical structure and materials of the microbubbles, as well as to methods for manufacturing microbubbles, methods for targeting microbubbles for specific medicinal applications, and methods for delivering microbubbles in medical treatment.

公开(公告)号：US20220211894A1

公开(公告)日：2022-07-07

申请号：US17524654

申请日：2021-11-11

Applicant: California Institute of Technology

Inventor： Robert H. GRUBBS ,  Carl M. BLUMENFELD ,  Harry B. GRAY ,  George R. ROSSMAN

IPC: A61L9/015 ,  A61L2/20 ,  B01J35/00 ,  B01J27/132 ,  B01J31/16 ,  C01B13/02

Abstract: Aspects disclosed herein include a system for generating singlet oxygen in a gas, the system comprising: a substrate; and hexanuclear clusters operably immobilized on at least a portion of the substrate; wherein each hexanuclear cluster comprises a photosensitive octahedral core complex characterized by formula FX1a: M6X8 (FX1a); wherein each M is independently Mo, W, or Re; wherein each X is independently a halide anion ligand; wherein the clusters are exposed to the gas and the gas comprises O2 gas; wherein the clusters are exposed to a light; and wherein each hexanuclear cluster is a photosensitizer configured to generate the gaseous singlet oxygen when irradiated by the light in the presence of the O2 gas.

公开(公告)号：US20210395463A1

公开(公告)日：2021-12-23

申请号：US17322250

申请日：2021-05-17

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Robert H. GRUBBS ,  Tzu-Pin LIN ,  Alice CHANG ,  Hsiang-Yun CHEN ,  Christopher M. BATES

IPC: C08G81/02 ,  C08F285/00 ,  C08F287/00 ,  C08G61/08 ,  C08F290/04 ,  C08F290/06 ,  C08F290/02

Abstract: In an aspect, a method of synthesizing a graft copolymer comprises the steps of: copolymerizing a first macromonomer and a first reactive diluent; wherein said first macromonomer comprises a first backbone precursor directly or indirectly covalently linked to a first polymer side chain group; wherein said reactive diluent is provided in the presence of the first macromonomer at an amount selected so as to result in formation said graft copolymer having a first backbone incorporating said diluent and said first macromonomer in a first polymer block characterized by a preselected first graft density or a preselected first graft distribution of said first macromonomer. In some embodiments of this aspect, said preselected first graft density is any value selected from the range of 0.05 to 0.75. In some methods, the composition and amount of said diluent is selected to provide both a first preselected first graft density and a first preselected first graft distribution.

公开(公告)号：US20210218063A1

公开(公告)日：2021-07-15

申请号：US17217428

申请日：2021-03-30

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY ,  HONDA MOTOR CO., LTD.

Inventor： Simon C. JONES ,  Victoria K. DAVIS ,  Christopher M. BATES ,  Nebojsa MOMCILOVIC ,  Brett M. SAVOIE ,  Michael A. WEBB ,  Thomas F. MILLER, III ,  Robert H. GRUBBS ,  Christopher BROOKS ,  Kaoru OMICHI

IPC: H01M10/0568 ,  H01M10/0525 ,  H01M10/0569 ,  H01M10/054 ,  C07C209/68

Abstract: Electrolyte solutions including at least one anhydrous fluoride salt and at least one non-aqueous solvent are presented. The fluoride salt includes an organic cation having a charge center (e.g., N, P, S, or O) that does not possess a carbon in the β-position or does not possess a carbon in the β-position having a bound hydrogen. This salt structure facilitates its ability to be made anhydrous without decomposition. Example anhydrous fluoride salts include (2,2-dimethylpropyl)trimethylammonium fluoride and bis(2,2-dimethylpropyl)dimethylammonium fluoride. Combining these fluoride salts with at least one fluorine-containing non-aqueous solvent (e.g., bis(2,2,2-trifluoroethyl)ether; (BTFE)) promotes solubility of the salt within the non-aqueous solvents. The solvent may be a mixture of at least one non-aqueous, fluorine-containing solvent and at least one other non-aqueous, fluorine or non-fluorine containing solvent (e.g., BTFE and propionitrile or dimethoxyethane). The electrolyte solutions may be employed in electrochemical cells, such as batteries, fuel cells, electrolysis systems, and capacitors.

公开(公告)号：US20200185776A1

公开(公告)日：2020-06-11

申请号：US16702327

申请日：2019-12-03

Applicant: HONDA MOTOR CO., LTD. ,  California Institute of Technology

Inventor： Qingmin XU ,  Christopher J. BROOKS ,  Kaoru OMICHI ,  Simon JONES ,  Victoria DAVIS ,  Stephen MUNOZ ,  Jeongmin KIM ,  Keith BILLINGS ,  Thomas MILLER, III ,  Robert H. GRUBBS ,  William WOLF

IPC: H01M10/0569 ,  H01M10/0567 ,  H01M6/16

Abstract: The present disclosure is directed to fluoride (F) ion batteries and F shuttle batteries comprising an anode with a solid electrolyte interphase (SEI) layer, a cathode comprising a core shell structure, and a liquid fluoride battery electrolyte. According to some aspects, the components therein enable discharge and recharge at room-temperature.

公开(公告)号：US20170275399A1

公开(公告)日：2017-09-28

申请号：US15398682

申请日：2017-01-04

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY ,  CORNELL UNIVERSITY

Inventor： Brett M. SAVOIE ,  Michael A. WEBB ,  Robert H. GRUBBS ,  Thomas F. MILLER, III ,  Geoffrey W. COATES ,  Qi ZHENG

IPC: C08F30/06 ,  C08K3/38 ,  C08K3/00

CPC classification number: C08F30/06 ,  C08G65/328 ,  C08K3/10 ,  C08K3/38 ,  C08K2003/0812 ,  C08L43/00 ,  C08L79/00 ,  C08L81/02 ,  C08L85/00 ,  C08L85/04 ,  C08L87/00 ,  H01M10/052 ,  H01M10/054 ,  H01M10/0565

Abstract: Anion-coordinating polymers comprising one or more anion-coordinating unit of Formula (I), optionally in combination with one or more cation-coordinating unit of Formula (II) and/or a linking unit of Formula (III) and related electrolytes, batteries, methods and system.

公开(公告)号：US20160237101A9

公开(公告)日：2016-08-18

申请号：US14461180

申请日：2014-08-15

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Robert H. GRUBBS ,  Matthias SCHOLL

IPC: C07F15/00

CPC classification number: C07F15/0046 ,  B01J31/2273 ,  B01J31/2278 ,  B01J31/2295 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C08G61/08

Abstract: The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are of the formula wherein: M is ruthenium or osmium; X and X1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R1, R6, R7, R8, and R9 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C2-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.

公开(公告)号：US20160215089A1

公开(公告)日：2016-07-28

申请号：US14915822

申请日：2014-09-04

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Robert TUBA ,  Robert H. GRUBBS

IPC: C08G61/08

CPC classification number: C08G61/08 ,  C08G61/12 ,  C08G2261/142 ,  C08G2261/1422 ,  C08G2261/3321 ,  C08G2261/3342 ,  C08G2261/418 ,  C08G2261/419 ,  C08G2261/724 ,  C08G2261/80 ,  C08L65/00

Abstract: This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

Abstract translation: 本发明涉及制备线性和环状聚烯烃的方法和组合物。 更具体地说，本发明涉及通过烯烃复分解反应制备官能化的直链和环状聚烯烃的方法和组合物。 通过本发明的烯烃复分解反应生产的聚合物产品可用于广泛的材料应用。 本发明在聚合物和材料化学和制造领域具有实用性。