Ruthenium complexes with diazadienes

Rohde, Wolfgang; Dieck, Heindirk tom

doi:10.1016/s0022-328x(00)99781-x

Cited by 9 publications

(12 citation statements)

References 36 publications

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“…This intermediate was then allowed to react with 2 equiv of SnClPh 3 , yielding the desired product. This method, which has also been used for the synthesis of [Ru(Me)(I)(CO) 2 (bpy)], , was also successfully used for the synthesis of [Ru(SnPh 3 ) 2 (CO) 2 (pAn-DAB)].…”

Section: Resultsmentioning

confidence: 99%

Tuning the Excited-State Properties of [M(SnR₃)₂(CO)₂(α-diimine)] (M = Ru, Os; R = Me, Ph)

Slageren

Stufkens

2000

Inorg. Chem.

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The influences of R, the alpha-diimine, and the transition metal M on the excited-state properties of the complexes [M(SnR3)2(CO)2(alpha-diimine)] (M = Ru, Os; R = Ph, Me) have been investigated. Various synthetic routes were used to prepare the complexes, which all possess an intense sigma-bond-to-ligand charge-transfer transition in the visible region between a sigma(Sn-M-Sn) and a pi*(alpha-diimine) orbital. The resonance Raman spectra show that many bonds are only weakly affected by this transition. The room-temperature time-resolved absorption spectra of [M(SnR3)2(CO)2(dmb)] (M = Ru, Os; R = Me, Ph; dmb = 4,4'-dimethyl-2,2'-bipyridine) show the absorptions of the radical anion of dmb, in line with the SBLCT character of the lowest excited state. The excited-state lifetimes at room temperature vary between 0.5 and 3.6 microseconds and are mainly determined by the photolability of the complexes. All complexes are photostable in a glass at 80 K, under which conditions they emit with very long lifetimes. The extremely long emission lifetimes (e.g., tau = 1.1 ms for [Ru(SnPh3)2(CO)2(dmb)]) are about a thousand times longer than those of the 3MLCT states of the [Ru(Cl)(Me)(CO)2(alpha-diimine)] complexes. This is due to the weak distortion of the former complexes in their 3SBLCT states as seen from the very small Stokes shifts. Remarkably, replacement of Ru by Os hardly influences the absorption and emission energies of these complexes; yet the emission lifetime is shortened because of an increase of spin-orbit coupling. The quantum yield of emission at 80 K is 1-5% for these complexes, which is lower than might be expected on the basis of their slow nonradiative decay.

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Section: Resultsmentioning

confidence: 99%

Tuning the Excited-State Properties of [M(SnR₃)₂(CO)₂(α-diimine)] (M = Ru, Os; R = Me, Ph)

Slageren

Stufkens

2000

Inorg. Chem.

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“…[36] [37] These homolysis reactions are assumed to co-workers [38] [39] , while the complexes have been used for The iPr-DAB ligand is σ(N1)Ϫσ(N2)-bonded to the ruthenium centre, just as in the case of [Ru(Me)(CO) 2 (iPran acylation reaction by Vrieze and co-workers. [40] [41] The related complexes [Ru(Cl) 2 (CO) 2 (α-diimine)] are known to DAB)] ϩ OTf Ϫ [43] , [Ru(I){C(O)Me}(CO) 2 (iPr-DAB)] [43] and [Ru(I)(Me)(iPr-DAB)(nbd)].…”

Section: (α-mentioning

confidence: 99%

Syntheses, Structures, and Spectroscopic Properties ofcis,cis-andtrans,cis-[Ru(I)(Me)(CO)2(α-diimine)] Complexes

Kleverlaan

Stufkens²,

Fraanje³

1998

Eur. J. Inorg. Chem.

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“…Main components (%) Transition energy a (eV) a 3 A (a 3 B 2 ) 47 (98a ->99a); 43 (93a ->99a); 1.53 (808) b 3 A (a 3 A 1 ) 95 (97a ->99a) 1.88 (660) a 3 A (a 3 B 2 ) 55 (93a ->99a); 31 (98a ->99a) 2.21 (562) b 3 A (a 3 A 2 ) 88 (98a ->100a) 2.49 (499) a wavelength in parenthesis Table S9. Selected structural parameters of the a 1 A (ground) and a 3 A (excited) states of [Ru(X) 2 (CO) 2 (Me-dab)].…”

Section: Statementioning

confidence: 99%

“…Herein, we have investigated photochemical CO dissociation from cis(CO,CO),trans(Cl,Cl) -[Ru(Cl) 2 (CO) 2 (iPr-dab)] (Figure ) using pico- and nanosecond TRIR. For comparison, we have also studied picosecond TRIR spectra of analogous complexes [Ru(I) 2 (CO) 2 (iPr-dab)] and the photostable ,,– , [Ru(Me)(I)(CO) 2 (iPr-dab)] and [Ru(SnPh 3 )(Cl)(CO) 2 (iPr-dab)], characterizing their lowest excited states. Stationary irradiation of [Ru(Cl) 2 (CO) 2 (iPr-dab)] leads to straight CO photosubstitution by a solvent molecule .…”

Section: Introductionmentioning

confidence: 99%

Nanosecond CO Photodissociation and Excited-State Character of [Ru(X)(X′)(CO)₂(N,N′-diisopropyl-1,4-diazabutadiene)] (X = X′ = Cl or I; X = Me, X′ = I; X = SnPh₃, X′ = Cl) Studied by Time-Resolved Infrared Spectroscopy and DFT Calculations

et al. 2008

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The character and dynamics of the low-lying excited states of [Ru(X)(X')(CO)2(iPr-dab)] (X=X'=Cl or I; X=Me, X'=I; X=SnPh3, X'=Cl; iPr-dab=N, N'-diisopropyl-1,4-diazabutadiene) were studied experimentally by pico- and nanosecond time-resolved IR spectroscopy (TRIR) and (for X=X'=Cl or I) computationally using density functional theory (DFT) and time-dependent DFT (TD-DFT) techniques. The lowest allowed electronic transition occurs between 390 and 460 nm and involves charge transfer from the Ru(halide)(CO) 2 unit to iPr-dab, denoted (1)MLCT/XLCT (metal-to-ligand/halide-to-ligand charge transfer). The lowest triplet state is well modeled by UKS-DFT-CPCM calculations, which quite accurately reproduce the excited-state IR spectrum in the nu(CO) region. It has a (3)MLCT/XLCT character with an intraligand (iPr-dab) (3)pipi* admixture. TRIR spectra of the lowest triplet excited state show two nu(CO) bands that are shifted to higher energies from their corresponding ground-state positions. The magnitude of this upward shift increases as a function of the ligands X and X' [(I)2 < (Sn)(Cl) < (Me)(I) < (Cl)2] and reveals increasing contribution of the Ru(CO)2-->dab MLCT character to the excited state. The lowest triplet state of [Ru(Cl)2(CO)2(iPr-dab)] undergoes a approximately 10 ps relaxation that is followed by CO dissociation, producing cis(CO,CH 3CN),trans(Cl,Cl)-[Ru(Cl)2(CH 3CN)(CO)(iPr-dab)] with a unity quantum yield and 7.2 ns lifetime and without any observable intermediate. To our knowledge, this is the first example of a "slow" CO dissociation from a thermally equilibrated triplet charge-transfer excited state.

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Ruthenium complexes with diazadienes

Cited by 9 publications

References 36 publications

Tuning the Excited-State Properties of [M(SnR₃)₂(CO)₂(α-diimine)] (M = Ru, Os; R = Me, Ph)

Tuning the Excited-State Properties of [M(SnR₃)₂(CO)₂(α-diimine)] (M = Ru, Os; R = Me, Ph)

Syntheses, Structures, and Spectroscopic Properties ofcis,cis-andtrans,cis-[Ru(I)(Me)(CO)2(α-diimine)] Complexes

Nanosecond CO Photodissociation and Excited-State Character of [Ru(X)(X′)(CO)₂(N,N′-diisopropyl-1,4-diazabutadiene)] (X = X′ = Cl or I; X = Me, X′ = I; X = SnPh₃, X′ = Cl) Studied by Time-Resolved Infrared Spectroscopy and DFT Calculations

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Ruthenium complexes with diazadienes

Cited by 9 publications

References 36 publications

Tuning the Excited-State Properties of [M(SnR3)2(CO)2(α-diimine)] (M = Ru, Os; R = Me, Ph)

Tuning the Excited-State Properties of [M(SnR3)2(CO)2(α-diimine)] (M = Ru, Os; R = Me, Ph)

Syntheses, Structures, and Spectroscopic Properties ofcis,cis-andtrans,cis-[Ru(I)(Me)(CO)2(α-diimine)] Complexes

Nanosecond CO Photodissociation and Excited-State Character of [Ru(X)(X′)(CO)2(N,N′-diisopropyl-1,4-diazabutadiene)] (X = X′ = Cl or I; X = Me, X′ = I; X = SnPh3, X′ = Cl) Studied by Time-Resolved Infrared Spectroscopy and DFT Calculations

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Tuning the Excited-State Properties of [M(SnR₃)₂(CO)₂(α-diimine)] (M = Ru, Os; R = Me, Ph)

Tuning the Excited-State Properties of [M(SnR₃)₂(CO)₂(α-diimine)] (M = Ru, Os; R = Me, Ph)

Nanosecond CO Photodissociation and Excited-State Character of [Ru(X)(X′)(CO)₂(N,N′-diisopropyl-1,4-diazabutadiene)] (X = X′ = Cl or I; X = Me, X′ = I; X = SnPh₃, X′ = Cl) Studied by Time-Resolved Infrared Spectroscopy and DFT Calculations