Synthesis and characterization of (nitro)ruthenium complexes that utilize identical trans-positioned tertiary phosphine ligands

Leising, Randolph A.; Kubow, Stephen A.; Takeuchi, Kenneth J.

doi:10.1021/ic00347a047

Cited by 20 publications

(7 citation statements)

References 4 publications

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“…We propose that the carbon directly bonded to the cluster (C α ) experiences long range coupling to the trans-phosphine ligand in compounds 1 and 2, leading to doublets with J CP values of 3.3 and 2.4, respectively. Longrange 13 C− 31 P coupling to trans-phosphines has been observed previously in mononuclear metal complexes, 32 but this is the first report of such coupling in these hexanuclear clusters. IR spectral data were obtained in order to examine the vibrational frequency of the acetylide bond.…”

Section: S Y N T H E S I Ssupporting

confidence: 54%

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

et al. 2022

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Three organometallic rhenium-based clusters containing phenylacetylide ligands, [Re 6 Se 8 (PEt 3 ) 5 (C�C−Ph)]-(SbF 6 ) (1) and cis-and trans-[Re 6 Se 8 (PEt 3 ) 4 (C�C−Ph) 2 ] (2 and 3), were synthesized and fully characterized including singlecrystal X-ray diffraction analyses. Reactivity studies of 1 show that reaction with electrophilic reagents does not result in the formation of the vinylidene species as predicted; instead, elimination of the acetylide moiety is observed. Products isolated from these r e a c t i o n s , i n c l u d i n g t h e m e t h y l s u l f a t e c o m p l e x , [Re 6 Se 8 (PEt 3 ) 5 (OSO 3 Me)](SbF 6 ) (4), have been characterized along with those obtained from the [2 + 2] cycloadditions of 1 with tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane. The relative reactivities of the electrophilic agents utilized are compared. Preliminary computational studies reveal useful information about the nature of the [Re 6 Se 8 ] 2+ −acetylide bond and aid in our understanding of the reactivity associated with this cluster complex.

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Section: S Y N T H E S I Ssupporting

confidence: 54%

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

et al. 2022

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“…The typical Ru-NO 2 frequencies of [3](ClO 4 ) appear at 1331 cm -1 (asymmetric) and 1288 cm -1 (symmetric). [15] The ν C=O band of bik and the perchlorate bands remain mostly invariant in the complexes; effects of coordination or reduction are small, in agreement with predominantly NO-centered electron transfer. Notably, the ν C=O frequency of coordinated bik in [4] 6 ) suggests an electrophilic character of the coordinated NO + group, as observed earlier in an analogous complex with 2,2Ј-dipyridyl ketone (ν NO frequency at 1949 cm -1 ).…”

Section: Spectroscopic Aspectsmentioning

confidence: 74%

Stabilization of {RuNO}⁶ and {RuNO}⁷ States in [Ru^II(trpy)(bik)(NO)]ⁿ⁺ {trpy = 2,2′:6′,2″‐terpyridine, bik = 2,2′‐bis(1‐methylimidazolyl) ketone} – Formation, Reactivity, and Photorelease of Metal‐Bound Nitrosyl

Sarkar

Maji

et al. 2009

Eur J Inorg Chem

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Ruthenium nitrosyl complexes have been isolated in the {RuNO}6 and {RuNO}7 configurations, employing the following reaction pathway for [Ru(trpy)(bik)(X)]n+: X = Cl–, [1](ClO4) → X = CH3CN, [2](ClO4)2 → X = NO2–, [3](ClO4) → X = NO+, [4](ClO4)3 → X = NO·, [4](ClO4)2. The single‐crystal X‐ray structures of [1](ClO4)·(C6H6)·H2O, [2](ClO4)2·H2O, and [3](ClO4)·H2O have been determined. The successive NO+/NO· (reversible) and NO·/NO– (irreversible) reduction processes of [4]3+ appear at +0.36 and –0.40 V vs. SCE, respectively. While the ν(C=O) frequency of the bik ligand at about 1630 cm–1 is largely invariant on complexation and reduction, the ν(NO) frequency for the {RuNO}6 state in [4]3+ at 1950 cm–1 shifts to about 1640 cm–1 on one‐electron reduction to the {RuNO}7 form in [4]2+, reflecting the predominant NO+ → NO· character of this electron transfer. However, a sizeable contribution from ruthenium with its high spin‐orbit coupling constant to the singly occupied molecular orbital (SOMO) is apparent from the enhanced g anisotropy in the EPR spectrum [4]2+ (g1 = 2.015, g2 = 1.995, g3 = 1.881; gav = 1.965; Δg = 0.134). The {RuNO}6 unit in [4]3+ reacts with OH– via an associatively activated process (ΔS# = –126.5 ± 2 J K–1 mol–1) with a second‐order rate constant of k = 3.3 × 10–2 M–1 s–1, leading to the corresponding nitro complex [3]+. On exposure to light both {RuNO}6 and {RuNO}7 in [4]3+ and [4]2+ undergo Ru–NO photocleavage in CH3CN via the formation of [Ru(trpy)(bik)(CH3CN)]2+, [2]2+. The rate of photocleavage of the RuII–NO+ bond in [4]3+ (kNO, 8.57 ×10–1 s–1, t1/2 = 0.80 s) is found to be much faster than that of the RuII–NO· bond in [4]2+, [kNO·, 5.45 × 10–4 s–1, t1/2 = 21.2 min (= 1272 s)]. The photoreleased nitrosyl can be trapped as an Mb‐NO adduct.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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“…2A, the UV region of Ru(terpy) PPh 3 has been ascribed to intraligand p ! p* transitions within both the terpyridine (terpy) and the triphenylphosphine ligands (PPh 3 ) [35,[39][40][41]. In the visible region, the lower energy absorption bands were assigned to metal-to-ligand charge transfer (MLCT) transitions which are predominantly Ru(dp) !…”

Section: Steady State Spectroscopymentioning

confidence: 99%

Investigation of the photophysical and eletrochemical properties of a free base tetrapyridyl porphyrin with meso carbon linked ruthenium(II) groups

Sampaio

Silva

Batista

et al. 2016

Journal of Photochemistry and Photobiology A: Chemistry

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Synthesis and characterization of (nitro)ruthenium complexes that utilize identical trans-positioned tertiary phosphine ligands

Cited by 20 publications

References 4 publications

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

Stabilization of {RuNO}⁶ and {RuNO}⁷ States in [Ru^II(trpy)(bik)(NO)]ⁿ⁺ {trpy = 2,2′:6′,2″‐terpyridine, bik = 2,2′‐bis(1‐methylimidazolyl) ketone} – Formation, Reactivity, and Photorelease of Metal‐Bound Nitrosyl

Investigation of the photophysical and eletrochemical properties of a free base tetrapyridyl porphyrin with meso carbon linked ruthenium(II) groups

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Synthesis and characterization of (nitro)ruthenium complexes that utilize identical trans-positioned tertiary phosphine ligands

Cited by 20 publications

References 4 publications

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

Stabilization of {RuNO}6 and {RuNO}7 States in [RuII(trpy)(bik)(NO)]n+ {trpy = 2,2′:6′,2″‐terpyridine, bik = 2,2′‐bis(1‐methylimidazolyl) ketone} – Formation, Reactivity, and Photorelease of Metal‐Bound Nitrosyl

Investigation of the photophysical and eletrochemical properties of a free base tetrapyridyl porphyrin with meso carbon linked ruthenium(II) groups

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Stabilization of {RuNO}⁶ and {RuNO}⁷ States in [Ru^II(trpy)(bik)(NO)]ⁿ⁺ {trpy = 2,2′:6′,2″‐terpyridine, bik = 2,2′‐bis(1‐methylimidazolyl) ketone} – Formation, Reactivity, and Photorelease of Metal‐Bound Nitrosyl