Structure and reactions of the thioether half-sandwich ruthenium(II) complexes [Ru(MeCN)3([9]aneS3)][CF3SO3]2 and [Ru(MeCN)2(PPh3)([9]aneS3)][CF3SO3]2([9]aneS3= 1,4,7-trithiacyclononane)

Landgrafe, Claudia; Sheldrick, William S.

doi:10.1039/dt9940001885

Cited by 55 publications

(60 citation statements)

References 16 publications

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“…1,8-Naphthalic anhydride, silver(I)sulfate and other chemicals were used as received from standard suppliers unless otherwise specified. 3-Bromo-1,8-naphthalic anhydride, 25 2-(trimethylstannyl)pyridine, 26 tetrakis(triphenylphosphine)-palladium(0), 27 [Ru(η 5 -C 5 H 5 )(CO)(MeCN) 2 ]PF 6 , 12 [Ru(MeCN) 3 ([9]aneS 3 )](CF 3 SO 3 ) 2 , 14 and [RuCl 2 (η 6 -C 6 H 6 )] 2 28 were prepared according to literature procedures. All solvents were distilled prior to use.…”

Section: Methodsmentioning

confidence: 99%

Organometallic Pyridylnaphthalimide Complexes as Protein Kinase Inhibitors

et al. 2011

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A new metal-containing scaffold for the design of protein kinase inhibitors is introduced. Key feature is a 3-(2-pyridyl)-1,8-naphthalimide “pharmacophore chelate ligand” which is designed to form two hydrogen bonds with the hinge region of the ATP-binding site and is at the same time capable of serving as a stable bidentate ligand through C-H-activation at the 4-position of the electron-deficient naphthalene moiety. This C-H-activation leads to a reduced demand for coordinating heteroatoms and thus sets the basis for a very efficient three-step synthesis starting from 1,8-naphthalic anhydride. The versatility of this ligand is demonstrated with the discovery of a ruthenium complex that functions as a nanomolar inhibitor for myosin light-chain kinase (MYLK or MLCK).

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Section: Methodsmentioning

confidence: 99%

Organometallic Pyridylnaphthalimide Complexes as Protein Kinase Inhibitors

et al. 2011

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“…As expected, the reactions are sluggish and conversions are slower when performed at r. t. Complexes 5a -b contain a dithiocarbamate ligand in an unusual η 1 -coordination mode (see below). Dithiocarbamate ligands are usually coordinated in an η 2 -fashion, both in poly- [9] and in mononuclear species [10]. The η 1 -mode is less common, and is mainly found in mononuclear compounds [11], whereas only few cases have been reported for polynuclear complexes [12,13].…”

Section: Substitution Reactions In Diiron and Diruthenium Aminocarbynmentioning

confidence: 99%

Synthesis and Characterization of New Diiron and Diruthenium μ-Aminocarbyne Complexes Containing Terminal S-, P- and C-Ligands

Albano

Busetto

Marchetti

et al. 2007

Zeitschrift Für Naturforschung B

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The diiron aminocarbyne complexes [Fe 2 {µ-CN(Me)(R)}(µ-CO)(CO)(NCMe)(Cp) 2 ][SO 3 CF 3 ] (R = Xyl, 1a; R = Me, 1b; R = CH 2 Ph, 1c; Xyl = 2,6-Me 2 C 6 H 3 ) undergo replacement of the coordinated nitrile by halides, diethyldithiocarbamate, and dicyanomethanide to give [Fe 2 {µ-CN(Me) (R)}(µ-CO)(CO)(X)(Cp) 2 ] complexes (R = Me, X = Br, 4a; R = Me, X = I, 4b; R = CH 2 Ph, X = Cl, 4c; R = CH 2 Ph, X = Br, 4d; R = CH 2 Ph, X = I, 4e; R = Xyl, X = SC(S)NEt 2 , 5a; R = Me, X = SC(S)NEt 2 , 5b; R = Xyl, X = CH(CN) 2 , 7), in good yields. The molecular structure of 5a shows an unusual η 1 coordination mode of the dithiocarbamate ligand.a series of phosphanes generates the cationic complexes [M 2 {µ-CN(Me)(R)}(µ-CO)(CO)(P)(Cp) 2 ][SO 3 CF 3 ] (M = Fe, R = Xyl, P = PPh 2 H, 6a; M = Fe, R = Xyl, P = PPh 3 , 6b; M = Fe, R = Xyl, P = PMe 3 , 6c; M = Fe, R = Me, P = PMe 2 Ph, 6d; M = Fe, R = Me, P = PPh 3 , 6e; M = Fe, R = Me, P = PMePh 2 , 6f; M = Ru, R = Xyl, P = PPh 2 H, 6g; M = Ru, R = Me, P = PPh 2 H, 6h), in high yields. The molecular structure of 6a has been elucidated by an X-ray diffraction study. The reactions of [Fe 2 {µ-CN(Me)(Xyl)}(µ-CO)(CO)(NCR )(Cp) 2 ][SO 3 CF 3 ] [R = Me, 1a; R = tBu, 3] with PhLi and PPh 2 Li yield [Fe 2 {µ-CN(Me)(Xyl)}(µ-CO)(CO)(Ph)(Cp) 2 ] (8) and [Fe 2 {µ-CN(Me)(Xyl)}(µ-CO)(CO)(PPh 2 )(Cp) 2 ] (9), respectively. The molecular structure of 8 has been ascertained by X-ray diffraction. Conversely, the reaction of 1a with MeLi generates the aminoalkylidene compound [Fe 2 {C(Me)N(Me)(Xyl)}(µ-CO) 2 (CO)(Cp) 2 ] (10). Finally, the acetone complex [Fe 2 {µ-CN(Me)(Xyl)}(µ-CO)(CO)(OCMe 2 )(Cp) 2 ][SO 3 CF 3 ] (12) reacts with lithium acetylides to give complexes [Fe 2 {µ-CN(Me)(Xyl)}(µ-CO)(CO)(C≡CR)(Cp) 2 ] (R = p-C 6 H 4 Me, 11a; R = Ph, 11b; R = SiMe 3 , 11c), in high yields. Filtration through alumina of a solution of 11a in CH 2 Cl 2 results in hydration of the acetylide group and C-Si bond cleavage, affording [Fe 2 {µ-CN(Me)(Xyl)}(µ-CO)(CO){C(O)Me}(Cp) 2 ] (12).

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“…We therefore decided to synthesize ruthenium pyridylphthalimide complexes containing the facial tridentate ligand 1,4,7-trithiacyclononane since it not only prevents the formation of diastereomers due to its high symmetry but we also expected that due to its bulkyness it would guide the cyclometalation to the C-5 position. Indeed, the reaction of the pyridylphthalimide ligands 2a or 2b with [Ru(MeCN) 3 ([9]aneS 3 )](CF 3 SO 3 ) 2 ( 6 ), 18 ([9]aneS 3 = 1,4,7-trithiacylononane) afforded the monoacetonitrile complexes 7a (79%) or 7b (74%), respectively, with high regioselectivity (Scheme 3). …”

Section: Resultsmentioning

confidence: 99%

“…Chemicals were used as received from standard suppliers. 2-(Trimethylstannyl)pyridine, 23 tetrakis (triphenylphosphine) palladium(0), 24 [Ir(COD)Cl] 2 , 25 [Ru( η 5 -C 5 H 5 )(CO)(MeCN) 2 ]PF 6 , 17 and [Ru(MeCN) 3 ([9]aneS 3 )](CF 3 SO 3 ) 2 ( 6 ) 18 were prepared according to literature procedures. Phthalimides 1a , 1b were synthesized according to modified literature procedures (see ESI for further details).…”

Section: Methodsmentioning

confidence: 99%

Bioactive cyclometalated phthalimides: design, synthesis and kinase inhibition

et al. 2012

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The regioselective cyclometalation of 4-(pyridin-2-yl)phthalimide was exploited for the economical design of organometallic protein kinase inhibitors. 4-(Pyridin-2-yl)phthalimide can be prepared from inexpensive 4-bromophthalimide in just three steps including one Pd-catalyzed Stille cross-coupling. The versatility of this new ligand was demonstrated with the synthesis of ruthenium(II) half-sandwich as well as octahedral ruthenium(II) and iridium(III) complexes. The regioselectivity of the C-H activation in the course of the cyclometalation can be influenced by the reaction conditions and the steric demand of the introduced metal complex fragment. The biological activity of this new class of metalated phthalimides was evaluated by profiling two representative members against a large panel of human protein kinases. A cocrystal structure of one metallo-phthalimide with the protein kinase Pim1 confirmed an ATP-competitive binding with the intended hydrogen bonding between the phthalimide moiety and the hinge region of the ATP-binding site.

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Structure and reactions of the thioether half-sandwich ruthenium(II) complexes [Ru(MeCN)3([9]aneS3)][CF3SO3]2 and [Ru(MeCN)2(PPh3)([9]aneS3)][CF3SO3]2([9]aneS3= 1,4,7-trithiacyclononane)

Cited by 55 publications

References 16 publications

Organometallic Pyridylnaphthalimide Complexes as Protein Kinase Inhibitors

Organometallic Pyridylnaphthalimide Complexes as Protein Kinase Inhibitors

Synthesis and Characterization of New Diiron and Diruthenium μ-Aminocarbyne Complexes Containing Terminal S-, P- and C-Ligands

Bioactive cyclometalated phthalimides: design, synthesis and kinase inhibition

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