Dialane with a Redox‐Active Bis‐amido Ligand: Unique Reactivity towards Alkynes

Fedushkin, Igor L.; Moskalev, M. V.; Lukoyanov, Anton N.; Tishkina, Alexandra N.; Баранов, Е. В.; Abakumov, G. A.

doi:10.1002/chem.201201364

Cited by 123 publications

(82 citation statements)

References 72 publications

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“…The addition of unsaturated compounds to metal–organic rings containing transition and main group metals is known . Such compounds as Ar 2 C=O, O 2 ,, CH 2 =CHC(O)CH 3 , and Ph 2 C=C=O, form cycloadducts with main group metal–organic rings.…”

Section: Resultsmentioning

confidence: 99%

“…The other mechanism was observed in the addition of alkynes to mono‐ and dinuclear gallium and aluminum complexes of the dianionic diimine ligands (path B) . Alkynes form cycloadducts with both L 1 and L 2 dialumanes and L 2 digallane 2 ,. However, such reactions were not observed for L 1 digallane 1 .…”

Section: Resultsmentioning

confidence: 99%

“…α‐Diimine ligands proved to be successful in stabilizing a variety of low‐valent metal complexes, including group 13 metal–metal‐bonded compounds such as digallanes and dialumanes –. These complexes have shown promising reactivity towards various small molecules, such as alkynes, alkenes, disulfides, azobenzenes, phenazine, sulfur dioxide, and ketone derivatives . Further, the α‐diimines are redox‐active ligands that can be easily oxidized or reduced, can serve as electron reservoirs, and allow significant extension of the reactivity of metal complexes.…”

Section: Introductionmentioning

confidence: 99%

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Cycloaddition versus Cleavage of the C=S Bond of Isothiocyanates Promoted by Digallane Compounds with Noninnocent α‐Diimine Ligands

Zhang

Dodonov

Chen

et al. 2018

Chemistry A European J

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Whereas the chemistry of single-bond activation by compounds of the main group elements has undergone some development in recent years, the cleavage of multiple bonds remains underexplored. Herein, the reactions of two digallanes bearing α-diimine ligands, namely, [L Ga-GaL ] (1, L =dpp-dad=[(2,6-iPr C H )NC(CH )] ) and [L Ga-GaL ] (2, L =dpp-bian=1,2-[(2,6-iPr C H )NC] C H ), with isothiocyanates are reported. Reactions of 1 or 2 with isothiocyanates in 1:2 molar ratio proceeded with [2+4] cycloaddition of the C=S bond across the C N Ga metallacycle with formation of C-C and S-Ga single bonds to afford [L (RN=C-S)Ga-Ga(S-C=NR)L ] (3, R=Me; 4, R=Ph) and [L (RN=C-S)Ga-Ga(S-C=NR)L ] (8, R=allyl; 9, R=Ph). In the cases of 8 and 9, this cycloaddition is reversible. The digallanes reacted with 2 equiv of PhNCS in the presence of Na metal or at high temperatures through a unique reductive cleavage of the C=S bond to yield the disulfide-bridged digallium species [Na(THF) ] [L Ga(μ-S) GaL ] (5), [L Ga(μ-S) GaL ] (10), and [Na(DME) ][L Ga(μ-S) GaL ] (11). Moreover, products 4 and 5 can further react with an excess of isothiocyanate, through cleavage of the C=S bond or cycloaddition, to give the bis- or mono-S-bridged complexes [Na(THF) ] [L (PhN=C-S)Ga(μ-S) Ga(S-C=NPh)L ] (6) and [L (PhN=C-S)Ga(μ-S)Ga(S-C=NPh)L ] (7). All the newly prepared compounds were characterized by elemental analysis, single-crystal X-ray diffraction, IR spectroscopy, NMR (3-9) or ESR spectroscopy (11), and DFT calculations.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cycloaddition versus Cleavage of the C=S Bond of Isothiocyanates Promoted by Digallane Compounds with Noninnocent α‐Diimine Ligands

Zhang

Dodonov

Chen

et al. 2018

Chemistry A European J

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“…The reversible addition of oxygen to the antimony catecholate and amidophenolate complexes [1][2][3][4][5] and the fixation of nitrogen monoxide by the lead and zinc catecholate complexes [6] were carried out. The gallium and aluminum complexes with the redox active diiminoacenaphthene ligand (BIAN) capable of activating the C≡C triple bond in alkynes were reported [7,8]. The possibility of haloid alkyl activation by the indium [9], gallium [10], and tin [11] о amidophenolate complexes was also shown.…”

Section: Introductionmentioning

confidence: 99%

New paramagnetic tin(IV) complexes based on o-iminoquinone ligands: Synthesis and thermal transformation

et al. 2015

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A series of new paramagnetic tin(IV) complexes based on sterically hindered o iminobenzoquino nes (R)ImQ differed in fragments (R) in the N aryl fragment is synthesized. The thermal transformation of the tin(IV) complex, (iso Pr)ImSQSn(tert Bu) 2 Cl ((iso Pr)ImSQ is the radical anion of 4,6 di tert butyl N (2,6 di iso propylphenyl) o iminobenzoquinone), is studied. The thermal transformation of the paramag netic complex in nonane results in the formation of a new tin(II) bis(aminophenolate) derivative. The syn thesized complexes and the thermolysis product are characterized by EPR, IR, and 1 H, 13 C, and 119 Sn NMR spectroscopy and elemental analysis. The structures of the (tert Bu)ImSQSn(tert Bu) 2 Cl complex and the thermal decomposition product, {(iso Pr)AmPh} 2 Sn ((iso Pr)AmPh is 2 (2,6 di iso propylphenyl)amino 4,6 di tert butylphenolate), are determined by X ray diffraction analysis.

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“…Structure of the complex (dpp bian)Cr(C 5 Me 5 )(8). Ther mal ellipsoids are drawn at 30% probability level.…”

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confidence: 99%

Compounds of chromium, titanium, and zirconium with different reduced forms of acenaphthene-1,2-diimine

et al. 2014

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The reaction of Cr(CO) 6 with 1,2 bis[(2,6 diisopropylphenyl)imino]acenaphthene (1, dpp bian) affords a chromium complex with the neutral diimine ligand (dpp bian)Cr(CO) 4 (2). The exchange reactions of the compound [(dpp bian)Cr( Cl)(THF)] 2 (3) with LiOH, PhCCNa, [(CH 3 ) 3 Si] 2 NK, C 5 H 5 Na, and C 5 Me 5 Na give the corresponding radical anion derivatives, viz., [(dpp bian)Cr( OH)] 2 (4), [(dpp bian)Cr( CCPh)] 2 (5), (dpp bian)Cr[N(SiMe 3 ) 2 ] (THF) (6), (dpp bian)Cr(C 5 H 5 ) (7), and (dpp bian)Cr(C 5 Me 5 ) (8). The titanium and zirconi um complexes with the acenaphthene 1,2 diimine dianion, viz., (dpp bian) 2 Ti (9) and (dpp bian)Zr(Cl)Cp (10), were synthesized by the reactions of Na 2 (dpp bian) with TiCl 4 and CpZrCl 3 , respectively. All compounds were characterized by IR spectroscopy and elemental analysis. Diamagnetic derivatives 2, 9, and 10 were additionally studied by 1 H NMR spectro scopy. The structures of products 2, 4-8, and 10 were determined by X ray diffraction.Key words: diimine ligands, transition metals, molecular and electronic structures.1,2 Bis(arylimino)acenaphthenes were put in use as ligands in the coordination chemistry about 10 years ago. 1,2 Bis[(2,6 diisopropylphenyl)imino]acenaphthene (1, dpp bian) is the most commonly applied ligand of this class. Its distinguishing features are, first, the conforma tional rigidity of the diimine moiety, the nitrogen atoms of which are coordinated to the metal atom, and, second, the shielding of the coordination area by bulky substituents at the nitrogen atoms. This ensures the formation of mono meric metal complexes, in which the diimine ligand never acts as a bridging ligand. The absolutely unique property of the dpp bian ligand is its ability to be reversibly reduced by alkali metals to mono , di , tri , and tetraanions to form the salts [(dpp bian) n-M + n (Et 2 O) m ] (M = Li, Na; n = 1-4, m = 1-4). 1,2 Organometallic compounds, for example, Me 2 Mg 3 or EtMgBr, 4 can also reduce dpp bian. In the former case, the reaction is accompanied by the elimination of the methyl radical to give the oragno magnesium derivative with the dpp bian radical anion [(dpp bian)MgMe] 2 . The reaction of dpp bian with a Grignard reagent affords the addition product of the oragnomagnesium compound at one of the C=N bonds of the diimine, (dpp bian Et)MgBr(Et 2 O) 2 . Both reactions proceed through the one electron transfer to form the dpp bian radical anion, which recombines with the ethyl radi cal to give the final product.A series of compounds containing unusual metal-met al bonds, including derivatives of Group 13 metals having unique reactivity toward alkynes, of the general formula (dpp bian)M-M(dpp bian) (M = Ga, Al) were synthe sized using dpp bian as the ligand. 5-9 Like other diimines, dpp bian can stabilize low oxidation states, including di valent states of silicon and germanium. 10-12 The redox isomerization in the complex of a 4f element, viz., in the compound [(dpp bian)YbBr(DME)] 2 , 13 was accom plished for the first time using the dpp b...

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Dialane with a Redox‐Active Bis‐amido Ligand: Unique Reactivity towards Alkynes

Cited by 123 publications

References 72 publications

Cycloaddition versus Cleavage of the C=S Bond of Isothiocyanates Promoted by Digallane Compounds with Noninnocent α‐Diimine Ligands

Cycloaddition versus Cleavage of the C=S Bond of Isothiocyanates Promoted by Digallane Compounds with Noninnocent α‐Diimine Ligands

New paramagnetic tin(IV) complexes based on o-iminoquinone ligands: Synthesis and thermal transformation

Compounds of chromium, titanium, and zirconium with different reduced forms of acenaphthene-1,2-diimine

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