Preparation of Cationic Dinuclear Hydrido Complexes of Ruthenium, Rhodium, and Iridium with Bridging Thiolato Ligands and Their Reactions with Nitrosobenzene

Iwasa, Takafumi; Shimada, Hitoshi; Takami, Atsushi; Matsuzaka, Hiroyuki; Ishii, Youichi; Hidai, Masanobu

doi:10.1021/ic981274e

Cited by 47 publications

(36 citation statements)

References 49 publications

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“…To our knowledge, apart from a special case, [6] type VIa is observed only in cationic dinuclear complexes of Rh with two further m 2 -thiolato bridges. [9] The complexes we reported recently [1] are the first simple, neutral and dinuclear C-nitroso complexes which have the rare, non-assisted m-h 1 :h 1 -N,O ligand function (type VIa) and only single atoms as additional bridges. Moreover, they have been synthesised directly from nitroso compounds as starting materials.…”

Section: Introductionmentioning

confidence: 93%

“…In the first series, the h 2 -N,O coordination mode (type I) [4] predominates over those with N (h 1 -N; type II) [5 6] or O coordination (h 1 -O; type III), [7] respectively. In the second series, the RNO ligand bridges two metal centres mainly (m-h 1 -N, type IV; [6] [6,9,10] m 2 -h 2 :h 2 -N,O, type VII [8c, 11] ). However, bridging as many as four metals (m 4 -h 2 :h 2 -NO, type VIII [12] ) is also possible.…”

Section: Introductionmentioning

confidence: 99%

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Dichroic, Dinuclear μ₂‐(η²‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)₃Re(μ‐X)}₂ONC₆H₄NR₂] (X = Cl, Br, I; R = Me, Et)

Krinninger

Högg

Nöth

et al. 2005

Chemistry A European J

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A series of unusual dinuclear mu2-(eta2-NO)-nitrosoaniline-bridged complexes [[(CO)3Re(mu-X)]2ONC6H4NR2] (X = Cl, Br, I; R = Me, Et) with dichroic properties have been synthesised by reaction of pentacarbonylhalogenorhenium(I) [(CO)5ReX] (X = Cl, Br, I) with the corresponding nitrosoaniline derivatives R2NC6H4NO (R = Me, Et). The deeply coloured solutions in CH2Cl2 show broad UV/Vis absorptions from 595 to 620 nm depending on the halogen bridges and N substituents. Single crystals of all six compounds exhibit a pronounced linear dichroism. The molecular structures have been determined by single-crystal X-ray analyses. All the compounds contain two face-shared octahedra, with two halogens and one NO ligand as bridges. The NO ligand coordinates in a nonsymmetrical eta2-like fashion with N or O coordination to each Re centre. Therefore, the C-nitroso group and the planar NC2 moiety of NR2 both lie almost exactly within the symmetry plane of the dinuclear complexes. These complexes belong to the novel and simple class of neutral dinuclear C-nitroso complexes that include the rare, non-assisted mu2-(eta2-NO) ligand function and have only single halogen atoms in bridging positions.

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Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Dichroic, Dinuclear μ₂‐(η²‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)₃Re(μ‐X)}₂ONC₆H₄NR₂] (X = Cl, Br, I; R = Me, Et)

Krinninger

Högg

Nöth

et al. 2005

Chemistry A European J

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“…The latter simply as a bridging ligand is less common; [11,14,15] most examples are known with supporting second coordination by a further donor system forming in addition a five-(VII) [16] or six-membered ring (VIII). [17] Only a few examples are known for bridging two metal atoms [µ 2 -(η 2 :η 2 -N,O), IX] [18] or four metal atoms .…”

Section: Introductionmentioning

confidence: 99%

“…[19] To the best of our knowledge type VI is only realized, besides a special case [11] in cationic dimers, with two further µ 2 -thiolato bridges. [14] …”

Section: Introductionmentioning

confidence: 99%

A New Dichroic, Nitroso‐Bridged Complex of Rhenium: Di‐μ₂‐chloro[μ₂‐(η²‐N,O)‐N,N‐dimethyl‐4‐nitrosoaniline]bis[tricarbonylrhenium(I)]

et al. 2004

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The dimeric μ2‐amino‐phenoxy complexes of rhenium [(CO)3Re(μ2‐O∩NH2)]2 (1) do not react with the C‐nitroso compounds R−C6H4NO [R = NMe2 (2), H (2′)] in the presence of AlCl3 by a condensation reaction to give the desired azo dye complexes [(CO)3Re(μ2‐O∩N=NC6H4R)]2. Instead, they react to give the novel neutral η2‐N,O‐bridged C‐nitroso complexes [{CO)3ReCl}2ONC6H4R] (3, 3′) by means of a substitution reaction. Both complexes yield golden gleaming crystals, and their solutions are deeply blue (3) or violet (3′) due to the broad UV/Vis absorption at λ = 617 (3) and 505 nm (3′). Single crystals of 3, 3′ show nonlinear optical properties, they are dichroic and have a red and blue (3) or violet and green (3′) side. The molecular structures of 3, 3′ have been determined by single‐crystal X‐ray analyses. Both compounds contain two face‐joined octahedra, with two chloro and the NO ligands as bridges. The C‐nitroso groups together with the NC2 moiety of NMe2 (3) lie almost exactly within the symmetry plane of the molecules. Both the N atoms of 3 have a trigonal‐planar geometry. 3 and 3′ are the first single, neutral and dinuclear C‐nitroso complexes with the rare non‐assisted μ‐(η2‐N,O) bridge and only single atoms as additional bridges. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…Ther oomtemperature EPR spectra of complexes 8-10 in toluene solution support this description and give rise to g iso values of 2.004, 2.008, and 2.005, respectively,i ndicative of organic radicals (see Figure 2C for the EPR spectrum of 8 and Figures S2.3 and S2.4 for the spectra of 9 and 10,r espectively). Notably,w hile persistent nitroxide radical complexes are uncommon, structurally characterized examples exhibiting k 1 -N, [36,38,39] k 1 -O, [40] and bridging m-(1k 1 -N:2k 1 -O) [41] coordination modes have been reported. However,c omplexes 8-10 are unique examples of side-on bound h 2 -N,O nitroxide radicals.…”

Section: Angewandte Chemiementioning

confidence: 99%

Kinetic Destabilization of Metal–Metal Single Bonds: Isolation of a Pentacoordinate Manganese(0) Monoradical

et al. 2015

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For decades,t ransiently generated 17e À monoradicals have occupied ac entral role in the development of atom-transfer and radical-mediated processes in organometallic chemistry. [1][2][3] Ap rototypical example of this class is the zerovalent manganese pentacarbonyl radical [Mn(CO) 5 ]which has been extensively investigated for its role in radical-type olefin hydrogenation, [4,5] [7][8][9][10] or at higher temperatures by using either ultrafast spectroscopic [11] or nitrosoarene spin-trapping techniques. [12][13][14] Importantly,efforts to prepare stabilized variants of [Mn(CO) 5 ]bysubstitution of one or more CO ligands with more encumbering ligands such as phosphines (PR 3 )h ave been shown to extend the lifetime of [MnL 5 ]-type radicals to the order of hours in solution. [15][16][17][18] However,such derivatized [Mn(CO) 5Àn L n ]c omplexes have remained susceptible to facile dimerization/redistributionp rocesses when concentrated and isolable examples remain unknown. Additionally, investigations into the one-electron activation chemistry of [Mn(CO) 5Àn L n ]s pecies with small molecule substrates are limited. [16,17] Given the challenges faced in exploring the properties of [Mn (CO) ) 2 ]( Ar Dipp2 = 2,6-(2,6-(iPr) 2 C 6 H 3 ) 2 C 6 H 3 )f eaturing two m-terphenyl isocyanide ligands. [22,23] Thesterically encumbering nature of these isocyanidel igands effectively prevents the formation of MnÀMn single bonds,thus rendering this 17eÀ radical both isolable in the solid state and persistent in solution. Additionally,asaresult of the isolobal analogy between carbon monoxide (CO) and organoisocyanides (C NR), [22,24] ) 2 ]delivers 1 most cleanly and in the highest yield after isolation (92 %; Figure 1A). Upon isolation, 1 is stable for days in solution at elevated temperatures (C 6 D 6 ,808 8C) and shows no sign of dimerization and/or ligand redistribution when concentrated to asolid.In both solution and the solid state,c omplex 1 possesses several spectroscopic and structural features consistent with ad 7 monoradical formulation. The 1 HNMR spectrum of 1 in C 6 D 6 features broad, shifted resonance signals characteristic of ap aramagnetic species,w hereas determination of the

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Preparation of Cationic Dinuclear Hydrido Complexes of Ruthenium, Rhodium, and Iridium with Bridging Thiolato Ligands and Their Reactions with Nitrosobenzene

Cited by 47 publications

References 49 publications

Dichroic, Dinuclear μ₂‐(η²‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)₃Re(μ‐X)}₂ONC₆H₄NR₂] (X = Cl, Br, I; R = Me, Et)

Dichroic, Dinuclear μ₂‐(η²‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)₃Re(μ‐X)}₂ONC₆H₄NR₂] (X = Cl, Br, I; R = Me, Et)

A New Dichroic, Nitroso‐Bridged Complex of Rhenium: Di‐μ₂‐chloro[μ₂‐(η²‐N,O)‐N,N‐dimethyl‐4‐nitrosoaniline]bis[tricarbonylrhenium(I)]

Kinetic Destabilization of Metal–Metal Single Bonds: Isolation of a Pentacoordinate Manganese(0) Monoradical

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Preparation of Cationic Dinuclear Hydrido Complexes of Ruthenium, Rhodium, and Iridium with Bridging Thiolato Ligands and Their Reactions with Nitrosobenzene

Cited by 47 publications

References 49 publications

Dichroic, Dinuclear μ2‐(η2‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)3Re(μ‐X)}2ONC6H4NR2] (X = Cl, Br, I; R = Me, Et)

Dichroic, Dinuclear μ2‐(η2‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)3Re(μ‐X)}2ONC6H4NR2] (X = Cl, Br, I; R = Me, Et)

A New Dichroic, Nitroso‐Bridged Complex of Rhenium: Di‐μ2‐chloro[μ2‐(η2‐N,O)‐N,N‐dimethyl‐4‐nitrosoaniline]bis[tricarbonylrhenium(I)]

Kinetic Destabilization of Metal–Metal Single Bonds: Isolation of a Pentacoordinate Manganese(0) Monoradical

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Dichroic, Dinuclear μ₂‐(η²‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)₃Re(μ‐X)}₂ONC₆H₄NR₂] (X = Cl, Br, I; R = Me, Et)

Dichroic, Dinuclear μ₂‐(η²‐NO)‐Nitrosoaniline‐Bridged Complexes of Rhenium of the Type [{(CO)₃Re(μ‐X)}₂ONC₆H₄NR₂] (X = Cl, Br, I; R = Me, Et)

A New Dichroic, Nitroso‐Bridged Complex of Rhenium: Di‐μ₂‐chloro[μ₂‐(η²‐N,O)‐N,N‐dimethyl‐4‐nitrosoaniline]bis[tricarbonylrhenium(I)]