Selective benzylic C–H activation of solvent toluene and m-xylene by an iron–tin cluster complex: Fe2(μ-)2(CO)8

Zhu, Li; Yempally, Veeranna; Isrow, Derek; Pellechia, Perry J.; Captain, Burjor

doi:10.1016/j.jorganchem.2009.09.024

Cited by 21 publications

(17 citation statements)

References 45 publications

(18 reference statements)

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“…The Sn II center in the anionic iron carbonyl complex 7 adopts a strongly distorted tetrahedral coordination environment with the Sn atom, the two Si substituents and the Fe atom almost in one plane (distance Sn/plane Si a 2 Fe: 41.4 pm) (Figure ). The Fe center shows a distorted trigonal‐bipyramidal configuration with an axial coordinated stannylene and a Sn−Fe bond (Sn−Fe 257.9 pm) characteristic for a Sn−Fe single bond (Sn−Fe: 250–265 pm from XRD,– 256 pm estimated from calculations). As a consequence of the coordination to the Fe(CO) 4 group the bonds of the Sn atom to the Si a and Cl atoms become slightly shorter compared to anion 1 (Table ).…”

Section: Resultssupporting

confidence: 48%

Cation‐Triggered Stannate(II)/Stannylenoid/Stannylene Conversion

Zhao

Xiao

et al. 2018

Chemistry A European J

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The reaction of dipotassio-tetrasilan-1,4-diide (4) with anhydrous SnCl at low temperature results in the formation of a five-membered cyclic potassio chlorostannate(II) ([(18-C-6)K](1)). By careful cation exchange reactions, it was transformed into the sodium chlorostannylenoid 2 (by using Na [B Cl ]) or into the non-stabilized cyclic bissilylstannylene 3 (through applying Li[Al(OC(CF ) ) ]). The increasing Lewis basicity of the bissilylstannylene 3 was analyzed by combined methods of DFT calculations and NMR spectroscopy and substantiated by the synthesis of the corresponding iron carbonyl complexes 7 and 8 from the chlorostannate 1 and the stannylene 3, respectively.

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Section: Resultssupporting

confidence: 48%

Cation‐Triggered Stannate(II)/Stannylenoid/Stannylene Conversion

Zhao

Xiao

et al. 2018

Chemistry A European J

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“…Related investigations of the coordination chemistry of Bu t 3 SnH with transition metals such as cobalt, nickel, and iron , have been reported earlier by our group. The current work began as part of an investigation of possible reaction mechanisms for the formation of complex 2 , one of which is shown in Scheme below.…”

Section: Introductionsupporting

confidence: 60%

“…3 ) 2 (CO) 2 , 23 and tri-tert-butylstannane, Bu t 3 SnH, 25,26 were prepared according to the published procedures.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis of [Pt(SnBu^t₃)(IBu^t)(μ-H)]₂, a Coordinatively Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt–Sn Complexes

et al. 2015

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The reaction of Pt(COD)2 with one equivalent of tri-tert-butylstannane, Bu(t)3SnH, at room temperature yields Pt(SnBu(t)3)(COD)(H)(3) in quantitative yield. In the presence of excess Bu(t)3SnH, the reaction goes further, yielding the dinuclear bridging stannylene complex [Pt(SnBu(t)3)(μ-SnBu(t)2)(H)2]2 (4). The dinuclear complex 4 reacts rapidly and reversibly with CO to furnish [Pt(SnBu(t)3)(μ-SnBu(t)2)(CO)(H)2]2 (5). Complex 3 reacts with N,N'-di-tert-butylimidazol-2-ylidene, IBu(t), at room temperature to give the dinuclear bridging hydride complex [Pt(SnBu(t)3)(IBu(t))(μ-H)]2 (6). Complex 6 reacts with CO, C2H4, and H2 to give the corresponding mononuclear Pt complexes Pt(SnBu(t)3)(IBu(t))(CO)(H)(7), Pt(SnBu(t)3)(IBu(t))(C2H4)(H)(8), and Pt(SnBu(t)3)(IBu(t))(H)3 (9), respectively. The reaction of IBu(t) with the complex Pt(SnBu(t)3)2(CO)2 (10) yielded an abnormal Pt-carbene complex Pt(SnBu(t)3)2(aIBu(t))(CO) (11). DFT computational studies of the dimeric complexes [Pt(SnR3)(NHC)(μ-H)]2, the potentially more reactive monomeric complexes Pt(SnR3)(NHC)(H) and the trihydride species Pt(SnBu(t)3)(IBu(t))(H)3 have been performed, for NHC = IMe and R = Me and for NHC = IBu(t) and R = Bu(t). The structures of complexes 3-8 and 11 have been determined by X-ray crystallography and are reported.

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“…The dinuclear oxidative addition reactions described here provide a basis for future investigation of the energetics of oxidative addition to mononuclear Pt and Pd complexes related to those recently shown to oxidatively activate dihydrogen and other small molecules. − The chemistry of stannyl radicals cannot be simply interpreted as being that of heavier analogues of carbon-based radicals. As illustrated in the review by Power, main group radicals, including stannyl radicals, have a rich and unique chemistry.…”

Section: Discussionmentioning

confidence: 99%

“…Recently in individual − and collaborative work, we reported investigations of use of the sterically demanding triorganotin hydride t Bu 3 SnH with transition metal complexes capable of small molecule activation. There is a rich history of synthesis of bulky tin ligands in the pioneering work of Neumann, Lappert, Davies, and others.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic, Kinetic, Structural, and Computational Studies of the Ph₃Sn–H, Ph₃Sn–SnPh₃, and Ph₃Sn–Cr(CO)₃C₅Me₅ Bond Dissociation Enthalpies

et al. 2016

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The kinetics of the reaction of PhSnH with excess •Cr(CO)CMe = •Cr, producing HCr and PhSn-Cr, was studied in toluene solution under 2-3 atm CO pressure in the temperature range of 17-43.5 °C. It was found to obey the rate equation d[PhSn-Cr]/dt = k[PhSnH][•Cr] and exhibit a normal kinetic isotope effect (k/k = 1.12 ± 0.04). Variable-temperature studies yielded ΔH = 15.7 ± 1.5 kcal/mol and ΔS = -11 ± 5 cal/(mol·K) for the reaction. These data are interpreted in terms of a two-step mechanism involving a thermodynamically uphill hydrogen atom transfer (HAT) producing PhSn• and HCr, followed by rapid trapping of PhSn• by excess •Cr to produce PhSn-Cr. Assuming an overbarrier of 2 ± 1 kcal/mol in the HAT step leads to a derived value of 76.0 ± 3.0 kcal/mol for the PhSn-H bond dissociation enthalpy (BDE) in toluene solution. The reaction enthalpy of PhSnH with excess •Cr was measured by reaction calorimetry in toluene solution, and a value of the Sn-Cr BDE in PhSn-Cr of 50.4 ± 3.5 kcal/mol was derived. Qualitative studies of the reactions of other RSnH compounds with •Cr are described for R = Bu,Bu, and Cy. The dehydrogenation reaction of 2PhSnH → H + PhSnSnPh was found to be rapid and quantitative in the presence of catalytic amounts of the complex Pd(IPr)(P(p-tolyl)). The thermochemistry of this process was also studied in toluene solution using varying amounts of the Pd(0) catalyst. The value of ΔH = -15.8 ± 2.2 kcal/mol yields a value of the Sn-Sn BDE in PhSnSnPh of 63.8 ± 3.7 kcal/mol. Computational studies of the Sn-H, Sn-Sn, and Sn-Cr BDEs are in good agreement with experimental data and provide additional insight into factors controlling reactivity in these systems. The structures of PhSn-Cr and CySn-Cr were determined by X-ray crystallography and are reported. Mechanistic aspects of oxidative addition reactions in this system are discussed.

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Selective benzylic C–H activation of solvent toluene and m-xylene by an iron–tin cluster complex: Fe2(μ-)2(CO)8

Cited by 21 publications

References 45 publications

Cation‐Triggered Stannate(II)/Stannylenoid/Stannylene Conversion

Cation‐Triggered Stannate(II)/Stannylenoid/Stannylene Conversion

Synthesis of [Pt(SnBu^t₃)(IBu^t)(μ-H)]₂, a Coordinatively Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt–Sn Complexes

Thermodynamic, Kinetic, Structural, and Computational Studies of the Ph₃Sn–H, Ph₃Sn–SnPh₃, and Ph₃Sn–Cr(CO)₃C₅Me₅ Bond Dissociation Enthalpies

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Selective benzylic C–H activation of solvent toluene and m-xylene by an iron–tin cluster complex: Fe2(μ-)2(CO)8

Cited by 21 publications

References 45 publications

Cation‐Triggered Stannate(II)/Stannylenoid/Stannylene Conversion

Cation‐Triggered Stannate(II)/Stannylenoid/Stannylene Conversion

Synthesis of [Pt(SnBut3)(IBut)(μ-H)]2, a Coordinatively Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt–Sn Complexes

Thermodynamic, Kinetic, Structural, and Computational Studies of the Ph3Sn–H, Ph3Sn–SnPh3, and Ph3Sn–Cr(CO)3C5Me5 Bond Dissociation Enthalpies

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Synthesis of [Pt(SnBu^t₃)(IBu^t)(μ-H)]₂, a Coordinatively Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt–Sn Complexes

Thermodynamic, Kinetic, Structural, and Computational Studies of the Ph₃Sn–H, Ph₃Sn–SnPh₃, and Ph₃Sn–Cr(CO)₃C₅Me₅ Bond Dissociation Enthalpies