Syntheses, structures and DFT study of [W(CO)5(Ph2SbX)] X=Cl, Br, I

Breunig, H. J.; Borrmann, Tobias; Lork, Enno; Raţ, Ciprian I.

doi:10.1016/j.jorganchem.2007.03.007

Cited by 10 publications

(11 citation statements)

References 34 publications

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“…The Ph 2 SbCl( L ) unit ( L = La and Lb ) may be interpreted as formal mono anionic ligand, and the Ph 2 SbCl unit may be interpreted as a neutral ligand at the (Ru 2 Cl 3 ) + core. Leong et al and Raţ et al reported the coordination behavior of Ph 2 SbCl toward osmium and tungsten. , Compounds 4a and 4b are the first examples of crystallographically characterized compounds with a Ph 2 ClSb–Ru motif . In spite of different (N,O)-bridging ligands, the Sb1–Ru1 bond lengths in 4a and 4b are very similar, whereas the Sb2–Ru2 bond lengths differ by about 0.02 Å.…”

Section: Resultsmentioning

confidence: 99%

“…Leong et al and Raţet al reported the coordination behavior of Ph 2 SbCl toward osmium and tungsten. 15,16 Compounds 4a and 4b are the first examples of crystallographically characterized compounds with a Ph 2 ClSb− Ru motif. 17 In spite of different (N,O)-bridging ligands, the Sb1−Ru1 bond lengths in 4a and 4b are very similar, whereas the Sb2−Ru2 bond lengths differ by about 0.02 Å.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E₂, and Tetradentate Sb,E₃ (E = N and O) Ligands and Their Reactivity Toward [RuCl₂(PPh₃)₃]

Gericke

Wagler

2020

Inorg. Chem.

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Neutral bi-, tri-, and tetradentate ligands of the type Ph3–x Sb(L) x [x = 1 (1), 2 (2), and 3 (3). L = La = phthalimidinyl (1a, 2a, and 3a), Lb = 2-pyridyloxy (1b, 2b, and 3b)] have been synthesized and characterized. Reaction of the Sb,E and Sb,E2 ligands with [RuCl2(PPh3)3] proceeded under anion scrambling with formation of complexes of type [Ph2Sb(μ-L)2Ru(PPh3)(μ-Cl)]2 (5) or [PhSb(μ-L)3RuCl(PPh3)] (8) in addition to various byproducts. Reactions of the Sb,E3 ligands and [RuCl2(PPh3)3] afforded highly diverse product mixtures. Deliberate syntheses of complexes of types 5 and 8 were successful by supplementing the reaction mixture with the required stoichiometric amount of either HLa or HLb and a supporting base. The Sb–Ru bonds, which are bridged by two (type 5) or three (type 8) phthalimidinyl or 2-pyridyloxy ligands, have been investigated using quantum chemical calculations at the DFT level (NBO/NLMO and AIM). Treatment of complexes of type 8 with fluoride ions resulted in the formation of compounds of type [PhFSb(μ-La)3RuL′(PPh3)] (L′ = O2 (9a-O 2 ), NCMe (9a-NCMe), or [PhFSb(μ-Lb)2Ru(κ2-Lb)(PPh3)] (10b)). In contrast to other similar bimetallic Sb-TM complexes (TM = transition metal), which may switch the rather dative intermetallic bond from Sb→TM to Sb←TM upon replacing TM bound chloride by Sb-bound fluoride, the character of the Sb→Ru bond is essentially retained upon going from chloro complex 5 or 8 to fluoro complex 9 or 10. Charge discrepancies caused by anion transfer from Ru to Sb are mainly compensated for by charge flow along the ligand backbone. All isolated complexes were characterized with multinuclear NMR spectroscopy, single-crystal X-ray diffraction, elemental analysis, and quantum chemical calculations.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E₂, and Tetradentate Sb,E₃ (E = N and O) Ligands and Their Reactivity Toward [RuCl₂(PPh₃)₃]

Gericke

Wagler

2020

Inorg. Chem.

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“…Lewis acid adducts include [SbMeCl 2 (2,2′bipy)], [SbPhX 2 (2,2′-bipy)], [SbPhX 2 (py) n ] ( n = 1 or 2), and [SbPh 2 X(2,2′-bipy)] . Lewis base behavior is found in [Cr(CO) 5 (SbMeCl 2 )], in [W(CO) 5 (SbPh 2 X)] (X = Cl, Br, or I), and in the unique example of a bidentate halostibine in [Rh{Ph 2 Sb(CH 2 ) 3 SbPh 2 }{PhClSb(CH 2 ) 3 SbClPh}Cl 2 ]Cl …”

Section: Introductionmentioning

confidence: 99%

Halostibines SbMeX₂ and SbMe₂X: Lewis Acids or Lewis Bases?

et al. 2012

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Alkylhalostibines have been shown to behave either as Lewis acids toward appropriate neutral ligands or as Lewis bases to low-valent metal fragments. The boundaries of their Lewis acid and Lewis base behavior have been determined, and the structural and spectroscopic consequences of the different behaviors probed. [SbMeX 2 (L−L)] (L−L = 2,2′-bipyridyl, 1,10-phenanthroline) and [SbMeX 2 (L) 2 ] (L = OPMe 3 , OPPh 3 ) are five-coordinate, distorted squarepyramidal monomers with the Me group axial, with the bond distances little affected by coordination. Significant changes in the bonding within the group 6 carbonyl complexes [M(CO) 5 (L′)] are evident, with L′→M σ-donation decreasing across the series L′ = SbMe 3 → SbMe 2 Br → SbMeBr 2 , and an increase in M→L′ π-acceptance within the same series. Intermolecular interactions are a major feature within these systems, ranging from weak, MCO•••Sb interactions in [M(CO) 5 (SbMe 2 Br)] and [M(CO) 5 (SbMeBr 2 )] to remarkably strong O•••Sb hypervalent bonds in [Mn(CO) 5 (SbMe 2 Br)][CF 3 SO 3 ] and [Mn(CO) 3 (SbMe 2 Br) 3 ][CF 3 SO 3 ], the latter involving the triflate anions. These lead to large changes in the geometry at Sb and represent very rare examples in which the antimony exhibits significant Lewis acid and Lewis base behavior simultaneously. The coordinated alkylhalostibines are alkylated cleanly with MeLi or n BuLi.

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“…A similar syn-syn conformation was observed for (Ph 2 Sb) 2 O [14] and (Me 2 Sb) 2 S, [12] whereas (R 2 Sb) 2 O (R = Me, [12] o-tolyl, p-tolyl [14] ) exhibit a syn-anti conformation. The molecular structure of 6 comprises a W(CO) 5 [26] The resulting coordination geometry around antimony is The five-membered SbC 3 N rings formed through intramolecular coordination of the nitrogen atoms in compounds 3-5 are folded along the Sb···C methylene axis, with the nitrogen atom lying out of the best plane defined by the residual SbC 3 fragment. This folding induces planar chirality (with the aromatic ring and the nitrogen atom as chiral plane and pilot atom, respectively; isomers given as S N and R N ) [27] as described for other related main-group metal compounds.…”

Section: Solid-state Structuresmentioning

confidence: 99%

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

et al. 2009

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Compounds containing the [2‐(Me2NCH2)C6H4]2Sb moiety were prepared by using R2SbX [X = Cl (1), Br (2)] as starting materials. The reaction of 1 with Me3SiCH2MgCl gave the mixed alkyl–aryl stibine R2SbCH2SiMe3 (3). Reduction of 2 with Mg in thf followed by in situ air oxidation or treatment with S8 resulted in the isolation of (R2Sb)2E [E = O (4), S (5)]. Compound 5 is also formed from R2SbCl and Na2S. The reaction of 4 with [W(CO)5(thf)] gives the unexpected complex [(R2SbOH)W(CO)5] (6). The new compounds were investigated by IR, 1H, and 13C NMR spectroscopy, as well as by mass spectrometry. The structures of 3–6 were determined by single‐crystal X‐ray diffraction. For compounds 3–5, both nitrogen atoms from the pendant arms are involved in intramolecular N→Sb coordination, which results in distorted square‐pyramidal (C,N)2SbC or (C,N)2SbE (E = O, S) cores. By contrast, in 6 only one nitrogen atom is strongly coordinated to the antimony center, whereas the second nitrogen atom is involved in N···H–O bonding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Syntheses, structures and DFT study of [W(CO)5(Ph2SbX)] X=Cl, Br, I

Cited by 10 publications

References 34 publications

Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E₂, and Tetradentate Sb,E₃ (E = N and O) Ligands and Their Reactivity Toward [RuCl₂(PPh₃)₃]

Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E₂, and Tetradentate Sb,E₃ (E = N and O) Ligands and Their Reactivity Toward [RuCl₂(PPh₃)₃]

Halostibines SbMeX₂ and SbMe₂X: Lewis Acids or Lewis Bases?

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

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Syntheses, structures and DFT study of [W(CO)5(Ph2SbX)] X=Cl, Br, I

Cited by 10 publications

References 34 publications

Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E2, and Tetradentate Sb,E3 (E = N and O) Ligands and Their Reactivity Toward [RuCl2(PPh3)3]

Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E2, and Tetradentate Sb,E3 (E = N and O) Ligands and Their Reactivity Toward [RuCl2(PPh3)3]

Halostibines SbMeX2 and SbMe2X: Lewis Acids or Lewis Bases?

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me2NCH2)C6H4]2Sb Fragment

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Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E₂, and Tetradentate Sb,E₃ (E = N and O) Ligands and Their Reactivity Toward [RuCl₂(PPh₃)₃]

Ruthenium Complexes of Stibino Derivatives of Carboxylic Amides: Synthesis and Characterization of Bidentate Sb,E, Tridentate Sb,E₂, and Tetradentate Sb,E₃ (E = N and O) Ligands and Their Reactivity Toward [RuCl₂(PPh₃)₃]

Halostibines SbMeX₂ and SbMe₂X: Lewis Acids or Lewis Bases?

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment