Structure and Reactivity of [Ru–Al] and [Ru–Sn] Heterobimetallic PPh3-Based Complexes
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PROVIDER: S-EPMC9554919 | biostudies-literature | 2022 Sep
REPOSITORIES: biostudies-literature
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Project description:A series of trans-RuL(PPh3)2(nitrile) and {RuL(PPh3)2}.2-μ-(nitrile)-based complexes [where L = 2,2'-(3,4-diphenyl-pyrrole-2,5-diyl)dipyridine (dpp), di(pyridin-2-yl)isoindoline-1,3-diimine (bpi), or 4-(4-methoxyphenyl)-6-phenyl-2,2'-bipyridine (Pbpy); and nitrile = 1,4-dibenzontirile, 4-ethynylbenzonitrile, or dicyanamide] were synthesized and characterized, and their electrochemical and photochemical behaviors were investigated. Those complexes that contained a significant nitrile contribution to their 3MLLCT show a release of their nitrile ligand (when L = dpp or Pbpy and the nitrile ligand = 4-dibenzontirile, or 4-ethynylbenzonitrile) with dissociation constants up to 8.09 × 10-4 s-1.
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Project description:A combined experimental and computational study of the structure and reactivity of two [RuZn2Me2] complexes, neutral [Ru(PPh3)(Ph2PC6H4)2(ZnMe)2] (2) and cationic [Ru(PPh3)2(Ph2PC6H4)(ZnMe)2][BArF4] ([BArF4] = [B{3,5-(CF3)2C6H3}4]) (3), is presented. Structural and computational analyses indicate these complexes are best formulated as containing discrete ZnMe ligands in which direct Ru-Zn bonding is complemented by weaker Zn···Zn interactions. The latter are stronger in 2, and both complexes exhibit an additional Zn···Caryl interaction with a cyclometalated phosphine ligand, this being stronger in 3. Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (PnBu3, PCy3, and IMes). With 3, all three Lewis bases result in the loss of [ZnMe]+. In contrast, 2 undergoes PPh3 substitution with PnBu3, but with IMes, loss of ZnMe2 occurs to form [Ru(PPh3)(C6H4PPh2)(C6H4PPhC6H4Zn(IMes))H] (7). The reaction of 3 with H2 affords the cationic trihydride complex [Ru(PPh3)2(ZnMe)2(H)3][BArF4] (12). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.
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Project description:Bimetallic active sites are ubiquitous in metalloenzymes and have sparked investigations of synthetic models to aid in the establishment of structure-function relationship. We previously reported a series of discrete bimetallic complexes with [FeIII-(μ-OH)-MII] cores in which the ligand framework provides distinct binding sites for two metal centers. The formation of these complexes relied on a stepwise synthetic approach in which an FeIII-OH complex containing a sulfonamido tripodal ligand served as a synthon that promoted assembly. We have utilized this approach in the present study to produce a new series of bimetallic complexes with [FeIII-(μ-OH)-MII] cores (M = Ni, Cu, Zn) by using an ancillary ligand to the FeIII center that contains phosphinic amido groups. Assembly began with formation of an FeIII-OH that was subsequently used to bind the MII fragment that contained a triazacyclononane ligand. The series of bimetallic complexes were charactered structurally by X-ray diffraction methods, spectroscopically by absorption, vibrational, electron paramagnetic resonance spectroscopies, and electrochemically by cyclic voltammetry. A notable finding is that these new [FeIII-(μ-OH)-MII] complexes displayed significantly lower reduction potentials than their sulfonamido counterparts, which paves way for future studies on high valent bimetallic complexes in this scaffold.
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Project description:Reaction of the known germylene Ge[N(SiMe3)2]2 and a new heterocyclic variant Ge[(NMes)2(CH)2] with [L(Me2)Cu]2 (L(Me2) = the beta-diketiminate derived from 2-(2,6-dimethylphenyl)amino-4-(2,6-dimethylphenyl)imino-2-pentene) yielded novel Cu(I)-Ge(II) complexes L(Me2)Cu-Ge[(NMes)2(CH)2] (1a) and L(Me2)Cu-Ge[N(SiMe3)2]2 (1b), which were characterized by spectroscopy and X-ray crystallography. The lability of the Cu(I)-Ge(II) bond in 1a and b was probed by studies of their reactivity with benzil, PPh3, and a N-heterocyclic carbene (NHC). Notably, both complexes are cleaved rapidly by PPh3 and the NHC to yield stable Cu(I) adducts (characterized by X-ray diffraction) and the free germylene. In addition, the complexes are highly reactive with O2 and exhibit chemistry which depends on the bound germylene. Thus, oxygenation of 1a results in scission and formation of thermally unstable L(Me2)CuO2, which subsequently decays to [(L(Me2)Cu)2(mu-O)2], while 1b yields L(Me2)Cu(mu-O)2Ge[N(SiMe3)2]2, a novel heterobimetallic intermediate having a [Cu(III)(mu-O)2Ge(IV)]3+ core. The isolation of the latter species by direct oxygenation of a Cu(I)-Ge(II) precursor represents a new route to heterobimetallic oxidants comprising copper.
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Project description:The syntheses, reactivity and electronic structure analyses of [Ru(PPh3 )2 (ZnMe)4 H2 ], 1 a, and [Ru(PPh3 )2 (ZnPh)4 H2 ], 2 b, are reported. 1 a exhibits an 8-coordinate Ru centre with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in 1 a undergo facile, sequential exchange with ZnPh2 to give 2 b, which shows a 3 : 1 arrangement of ZnPh ligands. Both 1 a and 2 b exist in equilibrium with their respective 3 : 1 and 2 : 2 isomers. Mechanisms for ZnMe/ZnPh exchange and isomerisation are proposed using DFT calculations. The relationships of these {Ru(ZnR)4 H2 } species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
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Project description:The successful architecture of active catalytic species with enhanced efficiencies is critical for the optimal exploitation of sustainable resources in industrially demanded processes. In this work, we describe the preparation of novel helical heterobimetallic Al/Mg-based complexes of the type [AlMe2(pbpamd-)MgR{κ1-O-(OC4H8O)}] [R = Et (1a), tBu (2a)] as potential catalysts. The design was performed through the sequential addition of the Al fragment to the ligand, followed by the Mg platform, resulting in a planar π-C2N2(sp2)-Al/Mg bridging core between metals. The new heterobimetallic species have been unambiguously characterized by single-crystal X-ray analysis. NOESY, DOSY, and EXSY NMR studies as well as density functional theory calculations corroborate both a rearrangement in solution to scorpionate complexes containing an unprecedented apical carbanion with a direct σ-C(sp3)-Al covalent bond named [{Mg(R)(pbpamd-) Al(Me)2}] [R = Et (1b), tBu (2b)] and an interconversion equilibrium between both isomers. We verified their utility and high efficiency as catalysts in the well-controlled ring-opening polymerization of the biorenewable l- and rac-lactide (LA) at 23 °C, reaching a remarkable turnover frequency value close to 25000 h-1 for rac-LA at this temperature and exerting a significant level of heteroselectivity (Pr = 0.80). Very interestingly, the kinetics demonstrate apparent first-order with respect to the catalyst and LA, which supports a synergic intramolecular cooperation between centers with electronic modulation among them.
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Project description:The interest for heterometallic lanthanide-d or-p metal (Ln-M) complexes is growing because of a potential cooperative or synergistic effect related to the proximity of two different metals in the same molecular architecture affording special tunable physical properties. To exploit the potentiality of Ln-M complexes, suitable synthetic approaches, and the in-depth understanding of the effect of each building block on their properties are mandatory. Here, we report the study on a family of heterometallic luminescent complexes [Ln(hfac)3Al(L)3], Ln= Eu3+ and Tb3+. Using different L ligands, we investigated the effect of the steric and electronic properties of the Al(L)3 fragment, highlighting the general validity of the employed synthetic route. A marked difference in the light emission of [Eu(hfac)3Al(L)3] and [Tb(hfac)3Al(L)3] complexes has been observed. Thanks to photoluminescence experiments and Density Functional Theory calculations, Ln3+ emissions are explained with a model involving two non-interacting excitation paths through hfac or Al(L)3 ligands.
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Project description: Not available
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Project description:A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2':6',2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI-TOF mass spectrometry, UV-Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311-577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications.
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Project description:[PdI 2(μ-PPh2)(μ2-OAc)(PPh3)2] is the reduction product of PdII(OAc)2(PPh3)2, generated by reaction of 'Pd(OAc)2' with two equivalents of PPh3. Here, we report that the reaction of [PdI 2(μ-PPh2)(μ2-OAc)(PPh3)2] with PPh3 results in a nuanced disproportionation reaction, forming [Pd0(PPh3)3] and a phosphinito-bridged PdI-dinuclear complex, namely [PdI 2(μ-PPh2){κ2-P,O-μ-P(O)Ph2}(κ-PPh3)2]. The latter complex is proposed to form by abstraction of an oxygen atom from an acetate ligand at Pd. A mechanism for the formal reduction of a putative PdII disproportionation species to the observed PdI complex is postulated. Upon reaction of the mixture of [Pd0(PPh)3] and [PdI 2(μ-PPh2){κ2-P,O-μ-P(O)Ph2}(κ-PPh3)2] with 2-bromopyridine, the former Pd0 complex undergoes a fast oxidative addition reaction, while the latter dinuclear PdI complex converts slowly to a tripalladium cluster, of the type [Pd3(μ-X)(μ-PPh2)2(PPh3)3]X, with an overall 4/3 oxidation state per Pd. Our findings reveal complexity associated with the precatalyst activation step for the ubiquitous 'Pd(OAc)2'/nPPh3 catalyst system, with implications for cross-coupling catalysis.
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