Electrochemical oxidation of cis-[Mo(CO)4(2,2′-bipyridine)] coupled with ligand substitution reactions in non-aqueous solvents

Hanzlík, Josef; Pospı́šil, Lubomı́r; Vlček, Antonı́n; Krejčík, Michael

doi:10.1016/0022-0728(92)85009-r

Cited by 14 publications

(11 citation statements)

References 28 publications

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“…[i] Not observed. [20,21] can be referred to a molybdenum-centered one-electron oxidation, [19] this process reveals a slight cathodic shift in 15 (Table 1, Figure 6). For the reduction of the 2,2Ј-bipyridyl ligand only one reduction process at -1.88 V is observed, whereby this process is cathodically shifted by 0.15 V upon σ-bonding of the alkynyl entity to the gold atom as given in 15.…”

Section: Electrochemistrymentioning

confidence: 97%

Mixed Heterotri‐ to Heteropentametallic Transition‐Metal Complexes: Synthesis, Characterization and Electrochemical Behavior

et al. 2008

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The synthesis and reaction chemistry of heteromultimetallic transition‐metal complexes are discussed. Complex [(η2‐dppf)(η5‐C5H5)Ru‐C≡C‐C6H4‐4‐PPh2] (3) [dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene], accessible by treating [(η2‐dppf)(η5‐C5H5)RuCl] (1) with equimolar amounts of HC≡C‐C6H4‐4‐PPh2 (2), gives on treatment with [(cod)RhCl]2 (4), [(η5‐C5Me5)RhCl2]2 (6), and [(tht)AuCl] (8) heterotrimetallic [(η2‐dppf)(η5‐C5H5)Ru‐C≡C‐C6H4‐4‐PPh2‐{Rh}] [5, {Rh} = (cod)RhCl; 7, {Rh} = (η5‐C5Me5)RhCl2] and [(η2‐dppf)(η5‐C5H5)Ru‐C≡C‐C6H4‐4‐PPh2‐AuCl] (9), respectively. Tetra‐ and even pentametallic heteronuclear complexes can be prepared by following consecutive reaction sequences: Treatment of 9 with HC≡CR {10a, R = C5H4N‐4; 10b, R = C6H4‐4‐C≡N; 10c, R = bpy (= 2,2′‐bipyridyl‐5‐yl); 12a, R = bpy[Re(CO)3Cl]} in the presence of HNEt2 and [CuI] gave [(η2‐dppf)(η5‐C5H5)Ru‐C≡C‐C6H4‐4‐PPh2‐Au‐C≡CR] {11a, R = C5H4N‐4; 11b, R = C6H4‐4‐C≡N; 11c, R = bpy; 13, R = bpy[Re(CO)3Cl]}. Compound 11c is the key starting material for complexes of higher nuclearity. Treatment of 11c with [(nbd)Mo(CO)4] (14) afforded heterotetrametallic {(η2‐dppf)(η5‐C5H5)Ru‐C≡C‐C6H4‐4‐PPh2‐Au‐C≡C‐bpy[Mo(CO)4]} (15), whereas with [{[Ti](μ‐σ,π‐C≡CSiMe3)2}M]X [16a, MX = Cu(N≡CMe)PF6; 16b, MX = AgOClO3] novel heteropentametallic [(η2‐dppf)(η5‐C5H5)Ru‐C≡C‐C6H4‐4‐PPh2‐Au‐C≡C‐bpy({[Ti](μ‐σ,π‐C≡CSiMe3)2}M)]X (17a, M = Cu, X = PF6; 17b, M = Ag, X = ClO4) is formed. The reaction of 11a with [{[Ti](μ‐σ,π‐C≡CSiMe3)2}Cu]OTf (16c) produced [(η2‐dppf)(η5‐C5H5)Ru‐C≡C‐C6H4‐4‐PPh2‐Au‐C≡C‐4‐C5H4N({[Ti](μ‐σ,π‐C≡CSiMe3)2}Cu)]OTf (18). The structures of 9, 11b, 11c, and 12 in the solid state and the electrochemical behavior of selected complexes are also reported.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Electrochemistrymentioning

confidence: 97%

Mixed Heterotri‐ to Heteropentametallic Transition‐Metal Complexes: Synthesis, Characterization and Electrochemical Behavior

et al. 2008

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“…V vs SCE, which possibly corresponds to a Mo-centered oxidation. 15 Note that, in the cyclic voltammograms of both 3 and 5, the two Fe-centered oxidations were barely separated (Figure 4), suggesting weak electronic coupling between the two redox centers. Complexation of the Mo center induced no significant changes in the electronic communication between the two organoiron end groups, as indicated by a negligible change in the peak separation (see the Supporting Information).…”

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confidence: 97%

“…Complexation of the Mo center to the bipy unit was clearly established by diagnostic ν C ⋮ O stretches, by the shift to more positive potentials of the Fe-centered oxidations for 5 relative to 3 (Δ E ° = 0.07 V) induced by the Lewis acidic nature of the Mo coordinated to the bipy unit in 5 12b and by the detection of a new pseudoreversible redox event near 0.74 V vs SCE, which possibly corresponds to a Mo-centered oxidation …”

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New Polypyridine Ligands Functionalized with Redox-Active Fe(II) Organometallic Fragments

et al. 2007

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We report in this Communication the isolation and characterization, including structure determinations, of 2,2',6',2"-terpyridine (2) and 2,2'-bipyridine (3) ligands bearing two redox-active "(eta2-dppe)(eta5-C5Me5)FeC[triple bond]C-" moieties grafted to the 5 and 5" positions of terpy or to the 5 and 5' positions of bipy. These "metalloligands" have been complexed with Ru(II) and Mo(0), providing new heterotrinuclear complexes displaying intense absorptions around 700 and 600 nm, respectively, for the Fe2Ru/terpy and Fe2Mo/bipy species. In both cases, the Fe(II)/Fe(III) oxidation potentials of the free ligands became more positive by more than 50 mV upon complexation.

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“…The Mo in complex 6 is more readily oxidized compared to the Mo center (E ox , 0.82 V) in Mo(CO) 4 (bipy) complex, 17 reflecting the electron-donating impact the Fc group.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Aminomethylation of Aminoferrocene, [(η⁵-C₅H₅)Fe(η⁵-C₅H₄NH₂)], and (Anilino)chromiumtricarbonyl, [(η⁶-C₆H₅NH₂)Cr(CO)₃], by O-Triethylsilyl-hemiaminal, (Et₃SiOCH₂NMe₂): The Role of Disparate Organometallic Electronic Effects in Modifying Product Outcomes

2022

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The room-temperature reaction of O-triethylsilyl-hemiaminal, Et 3 SiOCH 2 NMe 2 , (1) with primary amines containing organometallic electron-donating ferrocenyl or electron-withdrawing arenechromiumtricarbonyl groups, Fc−NH 2 {Fc = [(η 5 -C 5 H 5 )Fe(η 5 -C 5 H 4 )] (2) and [(η 6 -C 6 H 5 NH 2 )Cr(CO) 3 ] (3), respectively}, led to separate and distinctive chemistry. The reaction between 1 and 2 initially produced the transient triamine FcN(CH 2 NMe 2 ) 2 (4), which transformed upon workup into 1,3,5-triferrocenyl-1,3,5-hexahydrotriazine (5). The reaction between 1 and 3 led to the isolation of the diamine [(C 6 H 5 NHCH 2 NMe 2 )Cr(CO) 3 ] (7) as the only product. The complexes 5 and 7 are stable materials and were readily characterized spectroscopically and structurally. The labile ferrocenyltriamine 4 was readily trapped by complexation with Mo(CO) 4 {presented as [(norbornadiene)Mo(CO) 4 ]} to form [FcN(CH 2 (NMe 2 ) 2 ]Mo(CO) 4 (6), coordinating the Mo atom in a bidentate manner via the terminal NMe 2 groups. The Me 2 NCH 2 group in 7 readily exchanged upon reaction with either Et 2 NH or Et 2 NCH 2 NEt 2 to yield the diamine [(η 6 -C 6 H 5 NHCH 2 NEt 2 )Cr(CO) 3 ] (8). The initial cyclic voltammetric analysis exhibited oxidation of each separate metal center in both 5 and 6.

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Electrochemical oxidation of cis-[Mo(CO)4(2,2′-bipyridine)] coupled with ligand substitution reactions in non-aqueous solvents

Cited by 14 publications

References 28 publications

Mixed Heterotri‐ to Heteropentametallic Transition‐Metal Complexes: Synthesis, Characterization and Electrochemical Behavior

Mixed Heterotri‐ to Heteropentametallic Transition‐Metal Complexes: Synthesis, Characterization and Electrochemical Behavior

New Polypyridine Ligands Functionalized with Redox-Active Fe(II) Organometallic Fragments

Aminomethylation of Aminoferrocene, [(η⁵-C₅H₅)Fe(η⁵-C₅H₄NH₂)], and (Anilino)chromiumtricarbonyl, [(η⁶-C₆H₅NH₂)Cr(CO)₃], by O-Triethylsilyl-hemiaminal, (Et₃SiOCH₂NMe₂): The Role of Disparate Organometallic Electronic Effects in Modifying Product Outcomes

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Electrochemical oxidation of cis-[Mo(CO)4(2,2′-bipyridine)] coupled with ligand substitution reactions in non-aqueous solvents

Cited by 14 publications

References 28 publications

Mixed Heterotri‐ to Heteropentametallic Transition‐Metal Complexes: Synthesis, Characterization and Electrochemical Behavior

Mixed Heterotri‐ to Heteropentametallic Transition‐Metal Complexes: Synthesis, Characterization and Electrochemical Behavior

New Polypyridine Ligands Functionalized with Redox-Active Fe(II) Organometallic Fragments

Aminomethylation of Aminoferrocene, [(η5-C5H5)Fe(η5-C5H4NH2)], and (Anilino)chromiumtricarbonyl, [(η6-C6H5NH2)Cr(CO)3], by O-Triethylsilyl-hemiaminal, (Et3SiOCH2NMe2): The Role of Disparate Organometallic Electronic Effects in Modifying Product Outcomes

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Product

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Aminomethylation of Aminoferrocene, [(η⁵-C₅H₅)Fe(η⁵-C₅H₄NH₂)], and (Anilino)chromiumtricarbonyl, [(η⁶-C₆H₅NH₂)Cr(CO)₃], by O-Triethylsilyl-hemiaminal, (Et₃SiOCH₂NMe₂): The Role of Disparate Organometallic Electronic Effects in Modifying Product Outcomes