Dataset Information

Decarbonylative ether dissection by iridium pincer complexes.

ABSTRACT: A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported, mediated by iridium(i) complexes supported by aminophenylphosphinite (NCOP) pincer ligands. The decarbonylation, which involves the cleavage of one C-C bond, one C-O bond, and two C-H bonds, along with formation of two new C-H bonds, was serendipitously discovered upon dehydrochlorination of an iridium(iii) complex containing an aza-18-crown-6 ether macrocycle. Intramolecular cleavage of macrocyclic and acyclic ethers was also found in analogous complexes featuring aza-15-crown-5 ether or bis(2-methoxyethyl)amino groups. Intermolecular decarbonylation of cyclic and linear ethers was observed when diethylaminophenylphosphinite iridium(i) dinitrogen or norbornene complexes were employed. Mechanistic studies reveal the nature of key intermediates along a pathway involving initial iridium(i)-mediated double C-H bond activation.

SUBMITTER: Yoo C

PROVIDER: S-EPMC8162749 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Decarbonylative ether dissection by iridium pincer complexes.

Yoo Changho C Dodge Henry M HM Farquhar Alexandra H AH Gardner Kristen E KE Miller Alexander J M AJM

Chemical science 20200924 44

A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported, mediated by iridium(i) complexes supported by aminophenylphosphinite (NCOP) pincer ligands. The decarbonylation, which involves the cleavage of one C-C bond, one C-O bond, and two C-H bonds, along with formation of two new C-H bonds, was serendipitously discovered upon dehydrochlorination of an iridium(iii) complex containing an aza-18-crown-6 ether macrocycle. ...[more]

PMID: 34123222

Similar Datasets

Project description:The structure of [Ir{(4-Cl-C6H4N3)C(dppm)-κ3 P,C,N}(dppm-κ2 P,P')]Cl·1.5CH2Cl2·0.5C7H8 (C57H48Cl2IrN3P4·1.5CH2Cl2·0.5C7H8) (2), dppm = bis-(di-phenyl-phosphino)methane {systematic name: [7-(4-chloro-phen-yl)-1,1,3,3-tetra-phenyl-5,6,7-tri-aza-κN 7-1,3λ4-diphospha-κP 1-hepta-4,6-dien-4-yl][methyl-ene-bis(di-phenyl-phosphine)-κ2 P,P']iridium(I) chloride-di-chloro-methane-toluene (2/3/1)}, resulting from the reaction of [IrClH{C(dppm)2-κ3 P,C,P)(MeCN)]Cl (1a) with 1-azido-4-chloro-benzene, shows a monocationic five-coordinate IrI complex with a distorted trigonal-bipyramidal geometry. In 2, the iridium centre is coordinated by the neutral triazeneyl-idene-phospho-rane (4-Cl-C6H4N3)C(dppm) acting as a PCN pincer ligand, and a chelating dppm unit. The structure of the coordination compound [IrCl(CN)H(C(dppm)2-κ3 P,C,P)]·CH3CN, (C52H45ClIrNP4·CH3CN) (1b) [systematic name: chlorido-cyanidohydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,3λ5,5λ4,7-tetra-phospha-κ2 P 1,P 7-hept-3-en-4-yl)iridium(III) aceto-nitrile monosolvate], prepared from 1a and KCN, reveals an octa-hedral IrIII central atom with a meridional PCP pincer carbodi-phospho-rane (CDP) ligand; the chloride ligand is located trans to the central carbon of the CDP functionality while the hydrido and cyanido ligands are situated trans to each other. The chiral coordination compound [Ir(CN)((4-Cl-C6H4N3)CH(CH(P(Ph)2)2)-κ3 P,C,N)(dppm-κ2 P,P')]·2CH3OH, (C58H48ClIrN4P4·2CH3OH) (3) (systematic name: {4-[3-(4-chloro-phen-yl)triazenido-κN 3]-1,1,3,3-tetra-phenyl-1,3λ5-diphospha-κP 1-but-2-en-4-yl}cyanido[methyl-enebis(di-phenyl-phosphine)-κ2 P,P']iridium(III) methanol disolvate), formed via prolonged reaction of 1-azido-4-chloro-benzene with 1b, features a six-coordinate IrIII central atom. The iridium centre is coordinated by the dianionic facial PCN pincer ligand [(4-Cl-C6H4N3)CH(CH(P(Ph2)2)2)], a cyanido ligand trans to the central carbon of the PCN pincer ligand and a chelating dppm unit. Complex 2 exhibits a 2:1 positional disorder of the Cl- anion. The CH2Cl2 and C7H8 solvent mol-ecules show occupational disorder, with the toluene mol-ecule exhibiting additional 1:1 positional disorder with some nearly overlying carbon atoms.

Project description:Compound [Ir(C8H12)(C51H45P4)]Cl2 or [Ir(cod)(CH(dppm)2-κ3P,C,P)]Cl2 (1a), was obtained from [IrCl(cod)]2 and the carbodi-phospho-rane (CDP) salt [CH(dppm)2]Cl [where cod = cyclo-octa-1,5-diene and dppm = bis-(di-phenyl-phosphino)methane]. Treatment of 1a with thallium(I) tri-fluoro-methane-sulfonate [Tl(OTf)] and subsequent crystallization gave complex [Ir(C8H12)(C51H45P4)](OTf)2·CH3CO2C2H5·CH2Cl2 or [Ir(cod)(CH(dppm)2-κ3P,C,P)](OTf)2·CH3CO2C2H5·CH2Cl2 (1b) [systematic name: (cyclo-octa-1,5-diene)(1,1,3,3,5,5,7,7-octa-phenyl-1,7-diphospha-3,5-di-phospho-niaheptan-4-yl)iridium(I) bis-(tri-fluoro-methane-sulfonate)-ethyl acetate-di-chloro-methane (1/1/1)]. This five-coordinate iridium(I) complex cation adopts a trigonal-bipyramidal geometry with the CDP carbon and one cod double bond in axial sites. Compound 1b represents the first example of a non-meridional coordination of the PCP pincer ligand [CH(dppm)2]+ with a P-Ir-P angle of 98.08 (2)°. Compound 2, [IrCl2H(C51H44P4)]·(CH3)2CO or [IrCl2H(C(dppm)2-κ3P,C,P)]·(CH3)2CO [systematic name: di-chlorido-hydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,5λ5,7-triphospha-3-phospho-niahept-4-en-4-yl)iridium(III) acetone monosolvate], crystallizes as an acetone monosolvate. It is a six-coordinate IrIII coordination compound. Here, the PCP pincer ligand is coordinated in a meridional manner; one chlorido ligand is positioned trans to the carbon donor, the remaining two coordination sites being occupied by the second chlorido and a hydrido ligand trans to each other. Complex 3, [IrCl2H(C51H45P4)]Cl·5H2O or [IrCl2H(CH(dppm)2-κ3P,C,P)]Cl·5H2O [systematic name: di-chlorido-hydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,7-diphospha-3,5-di-phospho-niaheptan-4-yl)iridium(III) chloride penta-hydrate], represents the conjugate CH acid of 2. The ligand [CH(dppm)2]+ is coordinated in a meridional manner. In the cationic six-coordinate IrIII complex 4, [IrClH(CO)(C51H44P4)]Cl·2CH3OH·H2O or [IrClH(CO)(C(dppm)2-κ3P,C,P)]Cl·2CH3OH·H2O [systematic name: carbonyl-chlorido-hydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,5λ5,7-triphospha-3-phos-pho-niahept-4-en-4-yl)iridium(III) chloride-methanol-water (1/2/1)], the chlorido ligand is found in the plane defined by the Ir center and the meridional PCP ligand; the H and CO ligands are positioned axially to this plane and trans to each other.

Dataset Information

Decarbonylative ether dissection by iridium pincer complexes.

Publications

Decarbonylative ether dissection by iridium pincer complexes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets