Stacked complexes of iridium and a novel form of charge compensation

Rasmussen, Paul G.; Kolowich, J. Bruce; Bayón, Juan Carlos

doi:10.1021/ja00229a017

Cited by 18 publications

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“…A noticeable feature of the structure is also the association of two molecules through an Ir(d z 2 )–Ir(d z 2 ) interaction (Figure ) . The resulting dimer shows an intermolecular metal–metal distance of 3.1821(4) Å, which compares well with that reported for the anion [Ir(Tcbiim)(CO) 2 ] − (3.183(1) Å; Tcbiim = 4,4′,5,5′-tetracyano-2,2-biimidazolate) . The carbonyl ligands of one molecule eclipse the polycyclic system of the other molecule, whereas the lactamic four-membered rings are disposed in an antiparallel manner.…”

Section: Resultssupporting

confidence: 68%

Chelated Assisted Metal-Mediated N–H Bond Activation of β-Lactams: Preparation of Irida-, Rhoda-, Osma-, and Ruthenatrinems

et al. 2014

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2-Azetidinones substituted with pyridine (2a), quinoline (2b), isoquinoline (2c), imidazole (2d), and benzimidazole (2e) at the 4-position of the four-membered ring have been prepared in order to synthesize tribactams containing a transition metal and its associated ligands, L n M, at the 2-position of the tricyclic skeleton. The developed procedure is compatible with a wide range of transition-metal starting complexes. Thus, the iridium and rhodium dimers [M(η 5 -C 5 Me 5 )Cl 2 ] 2 react with 2a−e, in the presence of sodium acetate, to afford irida-and rhodatrinems (1a−j) containing the half-sandwich d 6 metal fragments M(η 5 -C 5 Me 5 )Cl (M = Ir, Rh). The reactions of [M(μ-OMe)(η 4 -COD)] 2 (M = Ir, Rh) with 2a lead to irida-and rhodatrinems (1k,l) with the d 8 moieties M(η 4 -COD). The coordination sphere and oxidation state of the metal center in these compounds can be modified, without affecting the 2-azetidinone backbone, by means of substitution and oxidative addition reactions. As a proof of concept, metallatrinems with the M(CO) 2 (M = Ir (1m), Rh (1n)) and Ir(Me)I(CO) 2 (1o) units are also reported. Osmatrinems 1p,q containing the d 4 metal fragment OsH 3 (P i Pr 3 ) 2 have been obtained starting from the d 2 hexahydride OsH 6 (P i Pr 3 ) 2 , by reaction with 2a,b, whereas the treatment of the tetrahydroborate complexes MH(η 2 -H 2 BH 2 )(CO)(P i Pr 3 ) 2 (M = Os, Ru) with 2a yields osma-and ruthenatrinems (1r,s) containing six-coordinate bis(phosphine) d 6 metal fragments. The IR stretching frequency of the lactamic carbonyl, the bent angle between the fiveand four-membered rings of the tricycle, and the N−CO bond length in the lactamic ring are clearly infuenced by the L n M fragment.

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Section: Resultssupporting

confidence: 68%

Chelated Assisted Metal-Mediated N–H Bond Activation of β-Lactams: Preparation of Irida-, Rhoda-, Osma-, and Ruthenatrinems

et al. 2014

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“…24 The red salts (Et 4 N)[Ir I (CO) 2 (Tcbiim)], (Et 2 Me 2 N)[Ir I (CO) 2 (Tcbiim)], and (Et 2 Me(CH 2 ) 4 NEt 2 MeN)-[Ir I (CO) 2 (Tcbiim)], where Tcbiim is the dianion 4,4′,5,5′-tetracyano-2,2′-biimidazolate, form extended stacks with Ir • • • Ir separations of 3.154, 3.206, and 3.159 Å, respectively, whereas the yellow salt (Et 3 MeN)-[Ir I (CO) 2 (Tcbiim)] appears to have no substantial metallophilic interactions with the closest contact between the iridium centers of 4.036 Å. 25 The shortest Ir • • • Ir distance in Ir I (CO) 2 Cl(pyrazine), which also forms extended stacks, is 3.579(3) Å. 26 The calculated densities of the polymorphs at 90(2) K reveal that the L. T. orange phase is the densest and thus the most efficiently packed, while the amber form is the least dense.…”

Section: Discussionmentioning

confidence: 99%

“…Racemic Ir I (CO) 2 (6-trifluoroacetylcarvonato) forms dimers with a Ir···Ir distance of 3.290(1) Å . The red salts (Et 4 N)[Ir I (CO) 2 (Tcbiim)], (Et 2 Me 2 N)[Ir I (CO) 2 (Tcbiim)], and (Et 2 Me(CH 2 ) 4 NEt 2 MeN)-[Ir I (CO) 2 (Tcbiim)], where Tcbiim is the dianion 4,4′,5,5′-tetracyano-2,2′-biimidazolate, form extended stacks with Ir···Ir separations of 3.154, 3.206, and 3.159 Å, respectively, whereas the yellow salt (Et 3 MeN)[Ir I (CO) 2 (Tcbiim)] appears to have no substantial metallophilic interactions with the closest contact between the iridium centers of 4.036 Å . The shortest Ir···Ir distance in Ir I (CO) 2 Cl(pyrazine), which also forms extended stacks, is 3.579(3) Å …”

Section: Discussionmentioning

confidence: 99%

Interplay of Supramolecular Organization, Metallophilic Interactions, Phase Changes, and Luminescence in Four Polymorphs of Ir^I(CO)₂(OC(CH₃)CHC(CH₃)N(p-tol))

et al. 2008

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Four polymorphs of IrI(CO)2(OC(CH3)CHC(CH3)N(p-tol)) have been characterized by single crystal X-ray crystallography. While all contain the same molecular unit with no significant structural variations within the molecules, all show different degrees of metallophilic interactions between the planar molecules. Three of these (the amber, the pale yellow, and the orange forms) are stable at room temperature, while the fourth, the L. T. orange form, is only obtained by cooling the orange polymorph. At 77 K, the amber, pale yellow, and L. T. orange polymorphs show intense luminescence. The variations in the luminescence among the polymorphs are considered in the context of the structural differences between them and the nature of the metallophilic interactions between the iridium centers. These results demonstrate how subtle variations in molecular organization can affect the physical properties of planar d8 transition metal compounds, which are an important class of lumiphores.

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“…In most cases, linear arrangement of C-N-M moiety is present, but incidental examples of side-on or bridging modes have been reported. 5 Cyano derivatized aromatic N-heterocycles, such as cyanopyridines, cyanobi-imidazoles 6,7,8,9 and cyanoimidazoles, are interesting candidates for the engineering of metal-organic frameworks. In these, the two types of nitrogen donors allow diverse reactivity and tailoring of the supramolecular structures.…”

Section: Introductionmentioning

confidence: 99%

Impacts of the counter ions on 4,5-dicyano-1-methylimidazole silver coordination

et al. 2018

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Stacked complexes of iridium and a novel form of charge compensation

Cited by 18 publications

References 0 publications

Chelated Assisted Metal-Mediated N–H Bond Activation of β-Lactams: Preparation of Irida-, Rhoda-, Osma-, and Ruthenatrinems

Chelated Assisted Metal-Mediated N–H Bond Activation of β-Lactams: Preparation of Irida-, Rhoda-, Osma-, and Ruthenatrinems

Interplay of Supramolecular Organization, Metallophilic Interactions, Phase Changes, and Luminescence in Four Polymorphs of Ir^I(CO)₂(OC(CH₃)CHC(CH₃)N(p-tol))

Impacts of the counter ions on 4,5-dicyano-1-methylimidazole silver coordination

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Stacked complexes of iridium and a novel form of charge compensation

Cited by 18 publications

References 0 publications

Chelated Assisted Metal-Mediated N–H Bond Activation of β-Lactams: Preparation of Irida-, Rhoda-, Osma-, and Ruthenatrinems

Chelated Assisted Metal-Mediated N–H Bond Activation of β-Lactams: Preparation of Irida-, Rhoda-, Osma-, and Ruthenatrinems

Interplay of Supramolecular Organization, Metallophilic Interactions, Phase Changes, and Luminescence in Four Polymorphs of IrI(CO)2(OC(CH3)CHC(CH3)N(p-tol))

Impacts of the counter ions on 4,5-dicyano-1-methylimidazole silver coordination

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Interplay of Supramolecular Organization, Metallophilic Interactions, Phase Changes, and Luminescence in Four Polymorphs of Ir^I(CO)₂(OC(CH₃)CHC(CH₃)N(p-tol))