Unprecedented spin localisation in a metal–metal bonded dirhenium complex

Yan, Yong; Mague, Joel T.; Donahue, James P.; Sproules, Stephen

doi:10.1039/c4cc09397f

Cited by 9 publications

(1 citation statement)

References 36 publications

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“…This molecule presumably forms via dissociation of mnt •– (Supporting Information, Figure S11) from one Rh center, after which the coordination sphere is filled via bridging S-ligation from an intact [Rh(mnt) 3 ] 3– . We note that this edge-sharing bioctahedral motif is rare–related species include Re and Mo tris(dithiolenes) as well as Co and Ru tris(dithiocarbamates). − In these cases, the coordination spheres are distorted from octahedral geometry, and the metrical parameters show evidence of metal–metal interactions. In 5 [ASN] 4 however, the octahedra are unperturbed, and the Rh···Rh distance of 3.5759(4) Å is inconsistent with a metal–metal interaction.…”

Section: Resultsmentioning

confidence: 96%

Stabilizing Coordinated Radicals via Metal–Ligand Covalency: A Structural, Spectroscopic, and Theoretical Investigation of Group 9 Tris(dithiolene) Complexes

et al. 2015

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Proper assignment of redox loci in coordination complexes with redox-active ligands to either the metal or the ligand is essential for rationalization of their chemical reactivity. However, the high covalency endemic to complexes of late, third-row transition metals complicates such assignments. Herein, we systematically explore the redox behavior of a series of group 9 tris(dithiolene) complexes, [M(mnt)3]3– (M = Ir, Rh, Co; mnt = maleonitriledithiolate). The Ir species described comprise the first examples of homoleptic Ir dithiolene complexes. The enhanced metal–ligand covalency of the Ir–S interaction leads to remarkable reactivity of [Ir(mnt)3]3– and stabilization of mononuclear [Ir(mnt)3]2– complex ions as well as dimerized versions featuring weak, covalent, intermolecular S–S bonds. The dianionic Rh and Co analogues are, in contrast, highly unstable, resulting in the rapid formation of [Rh2(mnt)5]4– and [Co(mnt)2]2 2–, respectively. The synthesized complexes were studied by single-crystal X-ray diffraction, X-ray absorption spectroscopy, optical spectroscopy, magnetometry, density functional theory, and spectroscopy-oriented configuration interaction calculations. Spectroscopic and theoretical analyses suggest that the stability of [Ir(mnt)3]2– may be attributed to dilution of ligand radical character by a high degree of Ir 5d character in the singly occupied molecular orbital.

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Section: Resultsmentioning

confidence: 96%

Stabilizing Coordinated Radicals via Metal–Ligand Covalency: A Structural, Spectroscopic, and Theoretical Investigation of Group 9 Tris(dithiolene) Complexes

et al. 2015

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Access to Stable Metalloradical Cations with Unsupported and Isomeric Metal–Metal Hemi‐Bonds

et al. 2015

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+ and trans-3C + in one crystal is unprecedented in the field of dinuclear metalloradical chemistry.The work suggests that more stable metalloradicals of metal-metal hemi-bonds may be accessible by using metal carbonyls together with large and weakly coordinating polyfluoroaluminate anions.Itisoffundamental importance to understand the nature of metal-metal bonds.[1] Compared with those supported by bridging ligands,unsupported metal-metal bonds are simpler and have attracted particular interest.[2] Understanding of the metal-metal interactions in the paramagnetic metal complexes is especially crucial for the fields of metalloproteins [3] and metal-containing functional materials.[4] An umber of supported dinuclear metalloradicals with two metal atoms held together to form ab ond by ab ridging ligand are known.[5] In contrast, stable but unsupported dinuclear metalloradicals are rare.Recently two unsupported dinuclear metalloradicals were isolated and studied by single crystal Xray diffraction, that is,[ M 2 Cp 2 (CO) 4 (PMe 3 ) 2 ]C + (M = Mo and W), where two metal atoms are held together by am ultiple bond (bond order = 1.5) with assistance from the electrondonating ligand PMe 3 .

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Access to Stable Metalloradical Cations with Unsupported and Isomeric Metal–Metal Hemi‐Bonds

et al. 2015

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Metalloradical species [Co2 Fv(CO)4 ](.+) (1(.+) , Fv=fulvalenediyl) and [Co2 Cp2 (CO)4 ](.+) (2(.+) , Cp=η(5) -C5 H5 ), formed by one-electron oxidations of piano-stool cobalt carbonyl complexes, can be stabilized with weakly coordinating polyfluoroaluminate anions in the solid state. They feature a supported and an unsupported (i.e. unbridged) cobalt-cobalt three-electron σ bond, respectively, each with a formal bond order of 0.5 (hemi-bond). When Cp is replaced by bulkier Cp* (Cp*=η(5) -C5 Me5 ), an interchange between an unsupported radical [Co2 Cp*2 (CO)4 ](.+) (anti-3(.+) ) and a supported radical [Co2 Cp*2 (μ-CO)2 (CO)2 ](.+) (trans-3(.+) ) is observed in solution, which cocrystallize and exist in the crystal phase. 2(.+) and anti-3(.+) are the first stable thus isolable examples that feature an unsupported metal-metal hemi-bond, and the coexistence of anti-3(.+) and trans-3(.+) in one crystal is unprecedented in the field of dinuclear metalloradical chemistry. The work suggests that more stable metalloradicals of metal-metal hemi-bonds may be accessible by using metal carbonyls together with large and weakly coordinating polyfluoroaluminate anions.

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Unprecedented spin localisation in a metal–metal bonded dirhenium complex

Abstract: [N(n-Bu)4]3[Re2(mnt)5] is the first class I, valence localized dirhenium(iii,iv) compound, with a metal–metal bond.

Cited by 9 publications

References 36 publications

Stabilizing Coordinated Radicals via Metal–Ligand Covalency: A Structural, Spectroscopic, and Theoretical Investigation of Group 9 Tris(dithiolene) Complexes

Stabilizing Coordinated Radicals via Metal–Ligand Covalency: A Structural, Spectroscopic, and Theoretical Investigation of Group 9 Tris(dithiolene) Complexes

Access to Stable Metalloradical Cations with Unsupported and Isomeric Metal–Metal Hemi‐Bonds

Access to Stable Metalloradical Cations with Unsupported and Isomeric Metal–Metal Hemi‐Bonds

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