Imperial College London

Dr Mark R. Crimmin

Faculty of Natural SciencesDepartment of Chemistry

Professor of Organometallic Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 2846m.crimmin Website

 
 
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Location

 

501NMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Publication Type
Year
to

151 results found

Gorgas N, White AJP, Crimmin MR, 2022, Diverse reactivity of an iron-aluminium complex with substituted pyridines, CHEMICAL COMMUNICATIONS, ISSN: 1359-7345

Journal article

Rekhroukh F, Zhang L, Kong RY, White AJP, Crimmin MRet al., 2022, Stereoselective insertion of cyclopropenes into Mg-Mg bonds, CHEMICAL COMMUNICATIONS, Vol: 58, Pages: 8282-8285, ISSN: 1359-7345

Journal article

Sheldon DJ, Crimmin MR, 2022, Repurposing of F-gases: challenges and opportunities in fluorine chemistry, CHEMICAL SOCIETY REVIEWS, Vol: 51, Pages: 4977-4995, ISSN: 0306-0012

Journal article

Gorgas N, White AJP, Crimmin MR, 2022, Cooperative C-H Bond Activation by a Low-Spin d(6) Iron-Aluminum Complex, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol: 144, Pages: 8770-8777, ISSN: 0002-7863

Journal article

Parr JM, White AJP, Crimmin MR, 2022, Magnesium-stabilised transition metal formyl complexes: structures, bonding, and ethenediolate formation, CHEMICAL SCIENCE, Vol: 13, Pages: 6592-6598, ISSN: 2041-6520

Journal article

Mulryan D, Rodwell J, Phillips NA, Crimmin MRet al., 2022, Au(I) Catalyzed HF Transfer: Tandem Alkyne Hydrofluorination and Perfluoroarene Functionalization, ACS CATALYSIS, Vol: 12, Pages: 3411-3419, ISSN: 2155-5435

Journal article

Batuecas M, Kong RY, White AJP, Crimmin MRet al., 2022, Functionalization and hydrogenation of carbon chains derived from CO, Angewandte Chemie International Edition, Vol: 61, ISSN: 1433-7851

Selective reactions that combine H 2 , CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C 3 and C 4 carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO) 6 ] and an aluminum(I) reductant, followed by functionalization and hydrogenation of the chain ends. A combination of kinetics (rates, KIEs) and DFT calculations has been used to gain insight into a key step which involves hydrogenation of a metallocarbene intermediate. These findings expand the extremely small scope of systems that combine H 2 and CO to make well-defined products with complete control over chain length and functionality.

Journal article

Kong RY, Batuecas M, Crimmin MR, 2021, Reactions of aluminium(i) with transition metal carbonyls: scope, mechanism and selectivity of CO homologation, CHEMICAL SCIENCE, Vol: 12, Pages: 14845-14854, ISSN: 2041-6520

Journal article

Brown R, Hooper TN, Rekhroukh F, White AJP, Costa PJ, Crimmin MRet al., 2021, Alumination of aryl methyl ethers: switching between sp 2 and sp 3 C–O bond functionalisation with Pd-catalysis, Chemical Communications, Vol: -, Pages: 1-4, ISSN: 1359-7345

The reaction of [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl) with aryl methyl ethers proceeded with alumination of the sp3 C–O bond. The selectivity of this reaction could be switched by inclusion of a catalyst. In the presence of [Pd(PCy3)2], chemoselective sp2 C–O bond functionalisation was observed. Kinetic isotope experiments and DFT calculations support a catalytic pathway involving the ligand-assisted oxidative addition of the sp2 C–O bond to a Pd–Al intermetallic complex.

Journal article

Crimmin MR, 2021, Benzene rings reach their breaking point, NATURE, Vol: 597, Pages: 33-34, ISSN: 0028-0836

Journal article

Sheldon DJ, Crimmin MR, 2021, Complete deconstruction of SF6 by an aluminium(i) compound, CHEMICAL COMMUNICATIONS, Vol: 57, Pages: 7096-7099, ISSN: 1359-7345

Journal article

Sheldon D, Crimmin M, 2021, Complete Deconstruction of SF6 by an Aluminium(I) Compound

<jats:p><jats:bold>The room-temperature activation of SF<jats:sub>6</jats:sub>, a potent greenhouse gas, is reported using a monovalent aluminium(I) reagent to form well-defined aluminium(III) fluoride and aluminium(III) sulfide products. New reactions have been developed to utilise the aluminium(III) fluoride and aluminium(III) sulfide as a nucleophilic source of F<jats:sup>–</jats:sup> and S<jats:sup>2– </jats:sup>for a range of electrophiles. The overall reaction sequence results in the net transfer of fluorine or sulfur atoms from an environmentally detrimental gas to useful organic products.</jats:bold></jats:p>

Journal article

Brown R, hooper TN, Rekroukh F, White AJP, Costa PJ, Crimmin Met al., 2021, Alumination of Aryl Methyl Ethers: Switching Between Sp2 and Sp3 C–O Bond Functionalisation with Pd-Catalysis, Publisher: American Chemical Society (ACS)

<jats:p>The reaction of [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl, 1) with aryl methyl ethers proceeded with alumination of the sp3 C–O bond by a presumed SN2 pathway. The selectivity of this reaction could be switched by inclusion of a catalyst. In the presence of [Pd(PCy3)2], chemoselective sp2 C–O bond functionalisation was observed. Kinetic isotope experiments and DFT calculations support a catalytic pathway involving the ligand-assisted oxidative addition of the sp2 C–O bond to a Pd---Al intermetallic complex. The net result of both non-catalysed and catalytic pathways is the generation of polar organoaluminium complexes from aryl methyl ethers with complete atom-efficiency. Switches in selectivity yield isomeric products from a single starting material. The methodology (and mechanistic insight) holds promise as a means to functionalise aromatic molecules derived from lignin depolymerisation and we demonstrate an application to a derivative of vanillin.</jats:p>

Working paper

Phillips N, Kong R, White A, Crimmin MRet al., 2021, Slippage between η2 and η1 coordination in Group 11 borataalkene complexes: models for alkene activation, Angewandte Chemie International Edition, Vol: 60, Pages: 12013-12019, ISSN: 1433-7851

A series of linear late transition metal (M = Cu, Ag, Au and Zn) complexes featuring a side-on [B=C] - containing ligand have been isolated and characterised. The [B=C] - moiety is isoelectronic with the C=C system of an alkene. Comparison across the series shows that in the solid-state, deviation between the η 2 and η 1 coordination mode occurs. The degree of slippage is greatest for Au > Ag > Cu. A related zinc complex containing two [B=C] - ligands was prepared as a further point of comparison for the η 1 coordination mode. The bonding in these new complexes has been interrogated by computational techniques (QTAIM, NBO, ETS-NOCV) and rationalised in terms of the Dewar-Chatt-Duncanson model. The combined structural and computational data provide unique insight into catalytically relevant linear d 10 complexes of Cu, Ag and Au. Slippage is proposed to play a key role in catalytic reactions of alkenes through disruption and polarisation of the p -system. Through the preparation and analysis of a consistent series of group 11 complexes, we show that variation of the metal can impact the degree of slippage and hence substrate activation.

Journal article

Phillips NA, Kong RY, White AJP, Crimmin MRet al., 2021, Group 11 Borataalkene Complexes: Models for Alkene Activation, Angewandte Chemie, Vol: 133, Pages: 12120-12126, ISSN: 0044-8249

Journal article

Kong RY, Crimmin MR, 2021, 1(st) row transition metal aluminylene complexes: preparation, properties and bonding analysis, Dalton Transactions: an international journal of inorganic chemistry, Vol: 50, Pages: 7810-7817, ISSN: 1477-9226

The synthesis and spectroscopic characterisation of eight new first-row transition metal (M = Cr, Mn, Fe, Co, Cu) aluminylene complexes is reported. DFT and ab initio calculations have been used to provide detailed insight into the metal–metal bond. The σ-donation and π-backdonation properties of the aluminylene ligand are evaluated via NBO and ETS-NOCV calculations. These calculations reveal that these ligands are strong σ-donors but also competent π-acceptors. These properties are not fixed but vary in response to the nature of the transition metal centre, suggesting that aluminylene fragments can modulate their bonding to accommodate both electron-rich and electron-poor transition metals. Ab initio DLPNO-CCSD(T) calculations show that dispersion plays an important role in stabilising these complexes. Both short-range and long-range dispersion interactions are identified. These results will likely inform the design of next-generation catalysts based on aluminium metalloligands.

Journal article

Kong RY, Crimmin M, 2021, 1st Row Transition Metal Aluminylene Complexes: Preparation, Properties and Bonding Analysis, Publisher: American Chemical Society (ACS)

<jats:p><jats:italic>The synthesis and spectroscopic characterisation of eight new first-row transition metal (M = Cr, Mn, Fe, Co, Cu) aluminylene complexes is reported. DFT and ab<jats:bold> </jats:bold>initio calculations have been used to provide detailed insight into the metal–metal bond. The σ-donation and π-backdonation properties of the aluminylene ligand are evaluated via NBO and ETS-NOCV calculations. These calculations reveal that these ligands are strong σ-donors but also competent π-acceptors. These properties are not fixed but vary in response to the nature of the transition metal centre, suggesting that aluminylene fragments can modulate their bonding to accommodate both electron-rich and electron-poor transition metals. Ab initio<jats:bold> </jats:bold>DLPNO-CCSD(T) calculations show that dispersion plays an important role in stabilising these complexes. Both short-range and long-range dispersion interactions are identified. These results will likely inform the design of next-generation catalysts based on aluminium metalloligands. </jats:italic></jats:p>

Working paper

Garçon M, Mun NW, White AJP, Crimmin MRet al., 2021, Palladium-catalysed C-H bond zincation of arenes: scope, mechanism, and the role of heterometallic intermediates, Angewandte Chemie International Edition, Vol: 60, Pages: 6145-6153, ISSN: 1433-7851

Catalytic methods that transform C-H bonds into C-X bonds are of paramount importance in synthesis. A particular focus has been the generation of organoboranes, organosilanes and organostannanes from simple hydrocarbons (X=B, Si, Sn). Despite the importance of organozinc compounds (X=Zn), their synthesis by the catalytic functionalisation of C-H bonds remains unknown. Herein, we show that a palladium catalyst and zinc hydride reagent can be used to transform C-H bonds into C-Zn bonds. The new catalytic C-H zincation protocol has been applied to a variety of arenes-including fluoroarenes, heteroarenes, and benzene-with high chemo- and regioselectivity. A mechanistic study shows that heterometallic Pd-Zn complexes play a key role in catalysis. The conclusions of this work are twofold; the first is that valuable organozinc compounds are finally accessible by catalytic C-H functionalisation, the second is that heterometallic complexes are intimately involved in bond-making and bond-breaking steps of C-H functionalisation.

Journal article

Garçon M, Mun NW, White AJP, Crimmin MRet al., 2021, Palladium‐Catalysed C−H Bond Zincation of Arenes: Scope, Mechanism, and the Role of Heterometallic Intermediates, Angewandte Chemie, Vol: 133, Pages: 6210-6218, ISSN: 0044-8249

Journal article

Batuecas M, Gorgas N, Crimmin MR, 2021, Catalytic C-H to C-M (M = Al, Mg) bond transformations with heterometallic complexes, CHEMICAL SCIENCE, Vol: 12, Pages: 1993-2000, ISSN: 2041-6520

Journal article

Kong RY, Crimmin MR, 2021, Chemoselective C-C σ-bond activation of the most stable ring in biphenylene., Angewandte Chemie International Edition, Vol: 60, Pages: 2619-2623, ISSN: 1433-7851

The chemoselective cleavage of a six-membered aromatic ring in biphenylene is reported using an aluminium(I) complex. This type of selectivity is unprecedented. In every example of transition metal mediated C-C sigma-bond activation reported to date, the reaction occurs at the central four-membered ring of biphenylene. Insight into the origin of chemoselecitivty was obtained through a detailed mechanistic analysis (isolation of an intermediate, DFT studies, activation strain analysis). We conclude that the divergent reactivity can be attributed to differences in both the symmetry and radial extension of the frontier molecular orbitals of the aluminium(I) fragment compared to common transition metal fragments.

Journal article

Kong RY, Crimmin MR, 2021, Chemoselective C−C σ‐Bond Activation of the Most Stable Ring in Biphenylene**, Angewandte Chemie, Vol: 133, Pages: 2651-2655, ISSN: 0044-8249

Journal article

Kong RY, Crimmin MR, 2020, Cooperative strategies for CO homologation, DALTON TRANSACTIONS, Vol: 49, ISSN: 1477-9226

Journal article

Mulryan D, White AJP, Crimmin MR, 2020, Organocatalyzed fluoride metathesis, Organic Letters, Vol: 22, Pages: 9351-9355, ISSN: 1523-7060

A new organocatalyzed fluoride metathesis reaction between fluoroarenes and carbonyl derivatives is reported. The reaction exchanges fluoride (F–) and alternate nucleophiles (OAc–, OCO2R–, SR–, Cl–, CN–, NCS–). The approach provides a conceptually novel route to manipulate the fluorine content of organic molecules. When the fluorination and defluorination steps are combined into a single catalytic cycle, a byproduct free and 100% atom-efficient reaction can be achieved.

Journal article

Sheldon DJ, Coates G, Crimmin MR, 2020, Defluorosilylation of trifluoromethane: upgrading an environmentally damaging fluorocarbon, CHEMICAL COMMUNICATIONS, Vol: 56, Pages: 12929-12932, ISSN: 1359-7345

Journal article

Kong RY, Crimmin M, 2020, Chemoselective C–C σ-Bond Activation of Biphenylene

<jats:p>The chemoselective cleavage of an arene ring in biphenylene is reported using an aluminium(I) complex. The reaction proceeds with complete integrity of the central 4-membered ring despite this ring containing the weakest C–C σ-bond in the hydrocarbon scaffold. A reaction intermediate derived from the (4+1) cycloaddition of the aluminium(I) complex to the p-system of biphenylene was isolated. Further experiments and DFT calculations suggest that this intermediate is involved in breaking of the C–C σ-bond. Activation strain analysis was used to understand the origins of the remarkable chemoselectivity of this system. Both the symmetry and diffuseness of the frontier molecular orbitals of the aluminium(I) fragment are implicated in its unusual reactivity with biphenylene.</jats:p>

Journal article

Crimmin M, Mulryan D, White AJP, 2020, Organocatalyzed Fluoride Metathesis

<jats:p>A new organocatalyzed fluoride metathesis reaction between fluoroarenes and carbonyl derivatives is reported. The reaction exchanges fluoride (F–) and alternate nucleophiles (OAc–, CO2R–, SR–, Cl–, CN–, NCS–). The approach provides a conceptually novel route to manipulate the fluorine content of organic molecules. By combining fluorination and defluorination steps into a single catalytic cycle, a byproduct free and 100% atom-efficient reaction can be achieved.</jats:p>

Journal article

Sheldon D, Coates G, Crimmin M, 2020, Defluorosilylation of Trifluoromethane: Upgrading an Environmentally Damaging Fluorocarbon

<jats:p>The rapid, room-temperature defluorosilylation of trifluoromethane, a highly potent greenhouse gas, has been achieved using a simple silyl lithium reagent. An extensive computational mechanistic analysis provides a viable reaction pathway and demonstrates the unexpected electrophilic nature of LiCF<jats:sub>3</jats:sub>. The reaction generates a bench stable fluorinated building block that shows promise as an easy-to-use difluoromethylating agent. The difluoromethyl group is an increasingly important bioisostere in active pharmaceutical ingredients, and therefore our methodology creates value from waste. The potential scalability of the process has been demonstrated by achieving the reaction on a gram-scale.</jats:p>

Journal article

Rekhroukh F, Chen W, Brown RK, White AJP, Crimmin MRet al., 2020, Palladium-catalysed C-F alumination of fluorobenzenes: mechanistic diversity and origin of selectivity, CHEMICAL SCIENCE, Vol: 11, Pages: 7842-7849, ISSN: 2041-6520

Journal article

Hooper TN, Brown RK, Rekhroukh F, Garcon M, White AJP, Costa PJ, Crimmin MRet al., 2020, Catalyst control of selectivity in the C-O bond alumination of biomass derived furans, CHEMICAL SCIENCE, Vol: 11, Pages: 7850-7857, ISSN: 2041-6520

Journal article

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