Klaus Jurkschat

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Organization: Technische Universit?t Dortmund , Germany

Department: Lehrstuhl für Anorganische Chemie II

Title: (PhD)

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Inorganic Chemistry

Chemicals
References

Introducing Stereogenic Centers to Group XIV Metallatranes

Co-reporter:Britta Glowacki, Michael Lutter, Hazem Alnasr, Rana Seymen, Wolf Hiller, and Klaus Jurkschat

Inorganic Chemistry May 1, 2017 Volume 56(Issue 9) pp:4937-4937

Publication Date(Web):April 10, 2017

DOI:10.1021/acs.inorgchem.6b03126

The syntheses of the novel amino alcohols NH(CH2CMe2OH)2(CMe2CH2OH) (1) and N(CH2CMe2OH)(CMe2CH2OH)(CH2CH2OH) (2) as well as the stannatranes N(CH2CMe2O)(CMe2CH2O)(CH2CH2O)SnX (3, X = Ot-Bu), N(CH2CMe2O)3SnOC(O)C9H13O2, 4, and germatranes N(CH2CMe2O)(CMe2CH2O)(CH2CH2O)GeX (5, X = OEt; 6, X = Br) are reported. The compounds were characterized by 1H, 13C (1–6), 119Sn (3, 4), and 15N (2, 3, 5) NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single crystal X-ray diffraction analysis. Graphset analyses were performed for compounds 1 and 2. Detailed NMR spectroscopic studies including variable temperature 1H (3, 5, 6) and 119Sn (3, 4) DOSY experiments reveal the stannatrane 3 being involved in a monomer–dimer equilibrium. Both the stannatranes 3 and 4 as well as the germatranes 5 and 6 show Λ ⇌ Δ isomerization of the atrane cages in solution.

It's Getting Tight: Highly Substituted Intramolecularly P=OSn Coordinated Ferrocene Derivatives

Co-reporter:Bastian Nayyar;Ramid Kapoor;Michael Lutter;Hazem Alnasr

European Journal of Inorganic Chemistry 2017 Volume 2017(Issue 33) pp:3967-3978

Publication Date(Web):2017/09/08

DOI:10.1002/ejic.201700914

Herein, we report the syntheses of the novel P(O)(OiPr)2- and organostannyl-substituted ferrocene derivatives Fe[{η5-C5H3-1-SnPh3-2-P(O)(OiPr)2}{η5-C5H4P(O)(OiPr)2}] (1a), Fe[η5-C5H3-1-SnPh3-2-P(O)(O-iPr)2]2 (1b), Fe[{η5-C5H2-1,3-(SnPh2X)2-2-P(O)(OiPr)2}{η5-C5H4P(O)(OiPr)2}] (2, X = I; 3, X = Br; 4, X = Cl; 5, X = F), and η5-CpFeη5-C5H-1,3-(SnPh3)2-4,5-[P(O)(OiPr)2]2 (7). Furthermore, we report the synthesis of the organotin iodide η5-CpFeη5-C5H-1,3-(SnPh2I)2-4,5-[P(O)(OiPr)2]2 (8), and its reactions with KF, AgPF6, I2, and AgClO4 to provide the corresponding organotin derivatives η5-CpFeη5-C5H-1,3-(SnPh2I)2-4,5-[P(O)(OiPr)2]2 (9), η5-CpFeη5-C5H-1,3-(SnPhI2)2-4,5-[P(O)(OiPr)2]2 (10), and [η5-CpFeη5-(C5H-1-SnPh2OH-3-SnPh2-4,5-{P(O)(OiPr)2}2)]ClO4·H2O (11). The latter compound is the first example of an air-stable, tetrasubstituted ferrocene derivative containing a bicentric (bis)organotin cation. The compounds were characterized by elemental analysis, 1H, 13C, 31P, 119Sn NMR and IR spectroscopy, electrospray ionization mass spectrometry, and, except for 6 and 9, single-crystal X-ray diffraction analysis.

Liquid membrane transport of potassium fluoride by the organotin-based ditopic host Ph2FSnCH2SnFPh-CH2-[19]-crown-6

Co-reporter:Alain Charly Tagne Kuate;Muhammad Moazzam Naseer

Chemical Communications 2017 vol. 53(Issue 12) pp:2013-2015

Publication Date(Web):2017/02/07

DOI:10.1039/C6CC09975K

The extraction of KF from aqueous media and transport through an organic membrane is extremely challenging owing to the high hydration energies of especially the F− anions. A novel organotin-based ditopic host containing the Ph2FSnCH2SnFPh-CH2-moiety (selective for fluoride anion complexation) covalently linked to 19-crown-6 (selective for potassium cation complexation) is reported. It transports KF up to 5.5- and 2.5-times faster than the dual-host mixture composed of the bidentate Lewis acid Ph2FSnCH2SnFPh2 and 18-crown-6 at low and high salt concentrations, respectively.

Organotin-based receptors for anions and ion pairs

Co-reporter:Muhammad Moazzam Naseer

Chemical Communications 2017 vol. 53(Issue 58) pp:8122-8135

Publication Date(Web):2017/07/18

DOI:10.1039/C7CC02667F

The field of anion recognition has developed into an area of tremendous significance over the recent decades due to the role of anions in biological and environmental systems, contributing significantly to the more general domain of supramolecular chemistry. So far, a number of receptors have been designed for anion recognition, synthesized and evaluated, most involving hydrogen bonding donors (urea, amide, pyrrole, imidazolium and hydroxyl groups), π-acidic aryl rings, Lewis acidic metals (boron, tin, aluminium, mercury and uranium) and positively charged polyammonium moieties. With the rapid progress in this field, the role of counterions in modulating the binding strength and selectivity of a specific ion has been recognized, leading to the design and discovery of more robust ion pair receptors. Among various recognition strategies that are presently available for anions and ion pairs, the development of Lewis acidic element-based receptors offers an attractive alternative to the hydrogen bond donor-based receptors, by which both anion and Lewis base recognition can be achieved. Consequently, researchers have focused a great deal of attention on such receptors and this sub-branch of recognition chemistry is expanding rapidly. In recent years, the desired selectivity and binding strength have been achieved for various anions by tuning the Lewis acidity through variation of substituents about the metal center. The easy access, rich molecular diversity and strong Lewis acidity of organotin compounds led to the development of organotin-based molecular receptors for anions and ion pairs. This feature article highlights the advances in the design, synthesis and applications of organotin-based receptors, mainly focusing on our group's contributions.

Novel Stannatrane N(CH2CMe2O)2(CMe2CH2O)SnO-t-Bu and Related Oligonuclear Tin(IV) Oxoclusters. Two Isomers in One Crystal

Co-reporter:Britta Glowacki, Michael Lutter, Dieter Schollmeyer, Wolf Hiller, and Klaus Jurkschat

Inorganic Chemistry 2016 Volume 55(Issue 20) pp:10218-10228

Publication Date(Web):September 27, 2016

DOI:10.1021/acs.inorgchem.6b01429

The syntheses of the alkanolamine N(CH2CMe2OH)2(CMe2CH2OH) (1), of the stannatrane N(CH2CMe2O)2(CMe2CH2O)SnO-t-Bu (2), and of the trinuclear tin oxocluster 3 consisting of the two isomers [(μ3-O)(O-t-Bu){Sn(OCH2CMe2)(OCMe2CH2)2N}3] (3a) and [(μ3-O)(μ3-O-t-Bu){Sn(OCH2CMe2)(OCMe2CH2)2N}3] (3b) as well as the isolation of a few crystals of the hexanuclear tin oxocluster [LSnOSn(OH)3LSnOH]2 [L = N(CH2CMe2O)2(CMe2CH2O)] (4) are reported. The compounds were characterized by 1H, 13C, 15N, and 119Sn (1–3) nuclear magnetic resonance and infrared spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis (1–4). A graph set analysis was performed for compound 1. The relative energies of 3a and 3b were estimated by density functional theory calculations that show that the energy differences are small.

Unsymmetrical Bicentric Organotin Lewis Acids {Me2N(CH2)3}Ph(X)Sn(CH2)nSnPh2X (X = F, I; n = 1, 3): Syntheses and Structures

Co-reporter:Nour Alashkar, Christina Dietz, Samer Baba Haj, Wolf Hiller, and Klaus Jurkschat

Organometallics 2016 Volume 35(Issue 16) pp:2738-2746

Publication Date(Web):August 8, 2016

DOI:10.1021/acs.organomet.6b00500

The syntheses of the intramolecularly coordinated organotin compounds {Me2N(CH2)3}Ph(X)SnCH2SnPh2X (3, X = I; 4, X = F) and {Me2N(CH2)3}Ph(F)Sn(CH2)3SnPh2F (7) are reported. The compounds have been characterized by elemental analysis, electrospray mass spectrometry, 1H,1H DOSY (4), 13C, 19F, and 119Sn NMR spectroscopy, and single-crystal X-ray diffraction analysis. In the solid state, compound 4 is a head-to-tail dimer as a result of unsymmetrical Sn–F–Sn bridges, whereas compound 7 is a monomer with F→Sn intramolecular coordination, giving a six-membered ring. In solution, both 4 and 7 are monomeric. The reactions of both 4 and 7 with fluoride anion in CD2Cl2 have been investigated by variable-temperature 19F and 119Sn NMR spectroscopy.

Silicon- and Tin-Containing Open-Chain and Eight-Membered-Ring Compounds as Bicentric Lewis Acids toward Anions

Co-reporter:Dr. Anicet Siakam Wendji;Dr. Christina Dietz;Dr. Silke Kühn;Michael Lutter;Dr. Dieter Schollmeyer;Dr. Wolf Hiller ;Dr. Klaus Jurkschat

Chemistry - A European Journal 2016 Volume 22( Issue 1) pp:404-416

Publication Date(Web):

DOI:10.1002/chem.201502722

Abstract

Herein, we report the syntheses of silicon- and tin-containing open-chain and eight-membered-ring compounds Me₂Si(CH₂SnMe₂X)₂ (2, X=Me; 3, X=Cl; 4, X=F), CH₂(SnMe₂CH₂I)₂ (7), CH₂(SnMe₂CH₂Cl)₂ (8), cyclo-Me₂Sn(CH₂SnMe₂CH₂)₂SiMe₂ (6), cyclo-(Me₂SnCH₂)₄ (9), cyclo-Me_(2−n)X_nSn(CH₂SiMe₂CH₂)₂SnX_nMe_(2−n) (5, n=0; 10, n=1, X=Cl; 11, n=1, X=F; 12, n=2, X=Cl), and the chloride and fluoride complexes NEt₄[cyclo- Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me⋅F] (13), PPh₄[cyclo-Me(Cl)Sn(CH₂SiMe₂CH₂)₂Sn(Cl)Me⋅Cl] (14), NEt₄[cyclo-Me(F)Sn(CH₂SiMe₂CH₂)₂Sn(F)Me⋅F] (15), [NEt₄]₂[cyclo-Cl₂Sn(CH₂SiMe₂CH₂)₂SnCl₂⋅2 Cl] (16), M[Me₂Si(CH₂Sn(Cl)Me₂)₂⋅Cl] (17 a, M=PPh₄; 17 b, M=NEt₄), NEt₄[Me₂Si(CH₂Sn(Cl)Me₂)₂⋅F] (18), NEt₄[Me₂Si(CH₂Sn(F)Me₂)₂⋅F] (19), and PPh₄[Me₂Si(CH₂Sn(Cl)Me₂)₂⋅Br] (20). The compounds were characterised by electrospray mass-spectrometric, IR and ¹H, ¹³C, ¹⁹F, ²⁹Si, and ¹¹⁹Sn NMR spectroscopic analysis, and, except for 15 and 18, single-crystal X-ray diffraction studies.

[Me2C{SnCH(SiMe3)2}2]2. A μ-Me2C-bridged tetrastanna tetrahedrane

Co-reporter:Michael Wagner, Michael Lutter, Bernhard Zobel, Wolf Hiller, Marc H. Prosenc and Klaus Jurkschat

Chemical Communications 2015 vol. 51(Issue 1) pp:153-156

Publication Date(Web):06 Nov 2014

DOI:10.1039/C4CC07417C

A spacer-bridged bis(organostannylene) was obtained. In the solid-state it adopts the structure of a doubly-capped tetrahedron. It reacts with elemental oxygen, O2, giving tin suboxides. Additionally, the first solid state structure of a spacer-bridged diorgano tin dihydride is reported.

N-Coordinated Tin(II) Trifluoromethanesulfonates and Their Reactions with Transition Metal Carbonyls

Co-reporter:Marek Bouska; Libor Dostál; Michael Lutter; Britta Glowacki; Zdenka Ruzickova; Daniel Beck; Roman Jambor

Inorganic Chemistry 2015 Volume 54(Issue 14) pp:6792-6800

Publication Date(Web):June 26, 2015

DOI:10.1021/acs.inorgchem.5b00678

The syntheses of the compounds [L1SnCl][M(CO)5(SnCl3)] (3, M = W; 4, M = Cr), [L1SnCl]OTf (5), [L1SnCl][W(CO)5(SnCl2OTf)] (6), [L1SnOTf][OTf] (7), and [L2Sn(OTf)2] (8) with L1 = {2,6-[(CH3)C═N(C6H3-2,6-iPr2)2]C5H3N} (DIMPY) and L2 = {2-[(CH3)C═N(C6H3-2,6-iPr2)]-6-(CH3O)}C5H3N) is reported. The compounds were characterized by elemental analyses, 1H, 13C, 19F, and 119Sn NMR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analyses (3·1.5C7H8, 5·CH2Cl2, 7·C7H8, 8). For compounds 7 and 8, the experimental work is accompanied by density functional theory calculations.

On the Reactivity of RSnCl and RSiMe3 {R = 4-tBu-2,6-[P(O)(OiPr)2]2C6H2} towards BF3OEt2: Competing Lewis Acidities

Co-reporter:Michael Wagner;Michael Lutter;Christina Dietz;Marc H. Prosenc

European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 12) pp:2152-2158

Publication Date(Web):

DOI:10.1002/ejic.201500014

Abstract

The reactions of boron trifluoride with the organostannylene RSnCl {R = 4-tBu-2,6-[P(O)(OiPr)₂]₂C₆H₂} and the organosilane RSiMe₃ provided the corresponding 1:1 and 1:2 complexes, respectively, through the formation of P=OB interactions. In the former reaction, even with excess BF₃·OEt₂, no SnB complexation involving the lone electron pair at the tin(II) center was observed. The experimental results are supported by DFT calculations.

Cyclic Dinuclear Organotin Cations Stabilized by Bulky Substituents

Co-reporter:Michael Wagner, Bernhard Zobel, Christina Dietz, Dieter Schollmeyer, and Klaus Jurkschat

Organometallics 2015 Volume 34(Issue 23) pp:5602-5608

Publication Date(Web):November 19, 2015

DOI:10.1021/acs.organomet.5b00829

The syntheses of sterically congested 2,2-bis(diorganochloridostannyl)propane, Me2C(SnClR2)2 (1; R = CH(SiMe3)2), the related salts [cyclo-{Me2C(SnR2)2X}B(ArF)4] (2, X = Cl; 3, X = OAc; 4, X = OH; ArF = 3,5-(CF3)2C6H3), and the four-membered-ring cyclo-{Me2C(SnR2)2O} (5) are reported. The compounds have been characterized by elemental and EDX analyses, 1H, 11B, 13C, 19F, 29Si, and 119Sn NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis.

cyclo-Stannasiloxanes Containing both Oxygen Atoms and Methylene Moieties within the Ring and Formation of Related Organotin Oxo Clusters

Co-reporter:Samer Baba Haj, Christina Dietz, Michael Lutter, and Klaus Jurkschat

Organometallics 2015 Volume 34(Issue 23) pp:5555-5565

Publication Date(Web):December 1, 2015

DOI:10.1021/acs.organomet.5b00768

The syntheses of the 8-membered stannasiloxanes cyclo-[RR′SnOSi(Me2)CH2]2 (5, R = R′ = Ph; 6, R = R′ = t-Bu; 7, R = Me2N(CH2)3, R′ = Ph) is reported. These react with organoelement oxides, providing the novel metallasiloxanes cyclo-[Me2SiCH2(RR′)SnOMO] (8, R = R′ = Ph, M = t-Bu2Sn; 9, R = R′ = t-Bu, M = t-Bu2Sn; 10, R = Me2N(CH2)3, R′ = Ph, M = t-Bu2Sn; 11, R = Me2N(CH2)3, R′ = Ph, M = Ph2Ge). Among these, compound 11 is the first example of such species being composed of four different group 14 elements in the 6-membered-ring skeleton. On contact with moist air compound 8 surprisingly undergoes Sn–Ph bond cleavage, giving the diorganotinoxo cluster [PhSn(CH2Me2SiO)Sn(μ3-O)(μ-OH)t-Bu2]2 (12), which shows a ladder-type structure. The latter reacts with 2 molar equiv of t-Bu2SnO, affording the Sn6-diorganotin oxo cluster [t-Bu2(μ-OH)Sn(μ3-O)SnPh(CH2Me2SiO)Sn-t-Bu2(μ3-O)]2 (13). The compounds have been characterized by NMR spectroscopy, electrospray mass spectrometry, and in the case of compounds 5–7, 12, and 13 also by single-crystal X-ray diffraction analysis.

Different Complexation Behavior of P-Functionalized Ferrocene Derivatives Towards SnCl2, SnCl4 and SnPh2Cl2: Auto-ionization and Redox-Type Reactions

Co-reporter:Dipl.-Chem. Matthias Gawron;Dr. Christina Dietz;Michael Lutter;Dr. Andrew Duthie;Dr. Viatcheslav Jouikov;Dr. Klaus Jurkschat

Chemistry - A European Journal 2015 Volume 21( Issue 46) pp:16609-16622

Publication Date(Web):

DOI:10.1002/chem.201501999

Abstract

The novel phosphonyl-substituted ferrocene derivatives [Fe(η⁵-Cp)(η⁵-C₅H₃{P(O)(O-iPr)₂}₂-1,2)] (Fc^1,2) and [Fe{η⁵-C₅H₄P(O)(O-iPr)₂}₂] (Fc^1,1′) react with SnCl₂, SnCl₄, and SnPh₂Cl₂, giving the corresponding complexes [(Fc^1,2)₂SnCl][SnCl₃] (1), [{(Fc^1,1′)SnCl₂}_n] (2), [(Fc^1,1′)SnCl₄] (3), [{(Fc^1,1′)SnPh₂Cl₂}_n] (4), and [(Fc^1,2)SnCl₄] (5), respectively. The compounds are characterized by elemental analyses, ¹H, ¹³C, ³¹P, ¹¹⁹Sn NMR and IR spectroscopy, ³¹P and ¹¹⁹Sn CP-MAS NMR spectroscopy, cyclovoltammetry, electrospray ionization mass spectrometry, and single-crystal as well as powder X-ray diffraction analyses. The experimental work is accompanied by DFT calculations, which help to shed light on the origin for the different reaction behavior of Fc^1,1′ and Fc^1,2 towards tin(II) chloride.

Organohydridosilanes containing Y,C,Y-chelating ligands: Reactivity and vapour pressure studies

Co-reporter:Miroslav Novák, Libor Dostál, Zdenka Padělková, Klaus Jurkschat, Christina Dietz, Květoslav Růžička, Michal Fulem, Antonín Lyčka, Roman Jambor

Journal of Organometallic Chemistry 2014 Volumes 772–773() pp:1-6

Publication Date(Web):1 December 2014

DOI:10.1016/j.jorganchem.2014.08.020

•Organohydridosilanes containing Y,C,Y-chelating ligands were prepared.•The vapour pressure was determined.•N → Si-coordinated silathiones and silaselenones were prepared.The syntheses of organohydridosilanes containing Y,C,Y-chelating ligands of the general formula PhL1-3SiH2 (1, L1 = C6H3(CH2OtBu)2-2,6; 2, L2 = C6H3(CH2OtBu)-2-(CH2NMe2)-6; 3, L3 = C6H3(CH2NMe2)2-2,6) are reported. The reactivity of compounds 1–3 towards elemental sulphur and selenium was studied. It depends on the identity of the donor atoms. While the ether-substituted organohydridosilane PhL1SiH2 (1) does not react, the amino-substituted organohydridosilanes PhL2SiH2 (2) and PhL3SiH2 (3) provide the N→Si-coordinated silathiones PhL2SiS (4), PhL3SiS (6) and the silaselenones PhL2SiSe (5), PhL3SiSe (7), respectively, all containing terminal Si–E bonds (E = S, Se). Compounds 1 and 2 do not react with water at ambient temperature whereas the hydrolysis of 3 yielded the diorganosilanediol PhL3Si(OH)2 (8). The compounds are characterized by 1H, 13C, 29Si, (1–8) and 77Se (6, 7) NMR spectroscopy and single crystal X-ray diffraction analysis (1, 8). In addition, the vapour pressures of compounds 2 and 3 were determined as well.The syntheses of organohydridosilanes containing Y,C,Y-chelating ligands of the general formula PhL1–3SiH2 (1, L1 = C6H3(CH2OtBu)2-2,6; 2, L2 = C6H3(CH2OtBu)-2-(CH2NMe2)-6; 3, L3 = C6H3(CH2NMe2)2-2,6) are reported. While PhL1SiH2 (1) is crystalline and molecular structure was determined by X-ray diffraction, the vapour pressures of oily compounds 2 and 3 were determined as well. In addition, the effect of the donor atoms upon the reactivity of organohydridosilanes 1–3 was studied further.

Syntheses and Molecular Structures of [RSn{W(CO)3Cp}2][W(CO)3Cp], [RSn{W(CO)3Cp}Cl2], and [RSn{W(CO)3Cp}Cr(CO)5] (R = [4-t-Bu-2,6-{P(O)(OR′)2}2C6H2], R′ = Et, i-Pr). Autoionization Induced by Intramolecular P═O→Sn Coordination

Co-reporter:Stefan Krabbe, Michael Wagner, Christian Löw, Christina Dietz, Markus Schürmann, Alexander Hoffmann, Sonja Herres-Pawlis, Michael Lutter, and Klaus Jurkschat

Organometallics 2014 Volume 33(Issue 17) pp:4433-4441

Publication Date(Web):August 21, 2014

DOI:10.1021/om500649d

The syntheses of the intramolecularly coordinated organotin-substituted transition metal complexes [RSn{W(CO)3Cp}2][W(CO)3Cp] (2, R = 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2), [RSn{W(CO)3Cp}Cl2] (4, R = 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2), and [RSn{W(CO)3Cp}Cr(CO)5] (5, R = 4-t-Bu-2,6-{P(O)(OEt)2}2C6H2) are reported. The reaction of compound 2 with Ph4P+Br¯ gave the benzoxaphosphastannole [1(P),3(Sn)-Sn[W(CO)3Cp]2OP(O)(Oi-Pr)-6-t-Bu-4-P(O)(Oi-Pr)2-C6H2] (3). The compounds are characterized by 1H, 13C, 31P, 119Sn NMR and IR spectroscopy and, except for 3, by single crystal X-ray diffraction analysis. The experimental work is accompanied by DFT calculations.

NHC to aNHC rearrangement by an organotin sulphide cation

Co-reporter:Michael Wagner, Thomas Zöller, Wolf Hiller, Marc H. Prosenc and Klaus Jurkschat

Chemical Communications 2013 vol. 49(Issue 79) pp:8925-8927

Publication Date(Web):08 Aug 2013

DOI:10.1039/C3CC45687K

An intramolecularly PO-coordinated dicationic diorganotin sulphide is presented. In solution, it shows a monomer–dimer equilibrium.

Novel Trialkanolamine Derivatives of Tin of the Type [N(CH2CMe2O)2(CH2)nOSnOR]m (m = 1, 2; n = 2, 3; R = t-Bu, 2,6-Me2C6H3) and Related Tri- and Pentanuclear Tin(IV) Oxoclusters. Syntheses and Molecular Structures

Co-reporter:Thomas Zöller and Klaus Jurkschat

Inorganic Chemistry 2013 Volume 52(Issue 4) pp:1872-1882

Publication Date(Web):January 31, 2013

DOI:10.1021/ic302042n

The syntheses of the novel alkanolamine N(CH2CMe2OH)2(CH2CH2CH2OH) (2), the novel aminotrialkoxides of tin of the type [N(CH2CMe2O)2(CH2)nOSnOR]m (3: m = 1, n = 2, R = t-Bu; 4: m = 2, n = 3, R = t-Bu; 5: m = n = 2, R = 2,6-Me2C6H3; 6: m = 2, n = 3, R = 2,6-Me2C6H3) and the related trinuclear tin oxoclusters [(LSnOSnL)(LSnOR)] [L = N(CH2CMe2O)2(CH2CH2O), 7: R = t-Bu; 8: R = 2,6-Me2C6H3] and the pentanuclear tin oxocluster [LSnOSn(OH)2OSnL·2LSnOH], [9, L = N(CH2CMe2O)2(CH2CH2O)] are reported. The compounds are characterized by elemental analyses, multinuclear (1H, 13C, 119Sn, 1H-1H cosy, 1H-13C HSQC) NMR spectroscopy, electrospray ionization mass spectrometry, and single crystal X-ray diffraction analyses (3, 4·C7H8, 5, 7, 8·0.5C7H8, 9·6H2O).

Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations

Co-reporter:Michael Wagner;Vajk Deáky;Christina Dietz;Jana Martincová;Bernard Mahieu;Roman Jambor;Sonja Herres-Pawlis

Chemistry - A European Journal 2013 Volume 19( Issue 21) pp:6695-6708

Publication Date(Web):

DOI:10.1002/chem.201203511

Abstract

The syntheses of the transition metal complexes cis-[(4-tBu-2,6-{P(O)(OiPr)₂}₂C₆H₂SnCl)₂MX₂] (1, M=Pd, X=Cl; 2, M=Pd, X=Br; 3, M=Pd, X=I; 4, M=Pt, X=Cl), cis-[{2,6-(Me₂NCH₂)₂C₆H₃SnCl}₂MX₂] (5, M=Pd, X=I; 6, M=Pt, X=Cl), trans-[{2,6-(Me₂NCH₂)₂C₆H₃SnI}₂PtI₂] (7) and trans-[(4-tBu-2,6-{P(O)(OiPr)₂}₂ C₆H₂SnCl)PdI₂]₂ (8) are reported. Also reported is the serendipitous formation of the unprecedented complexes trans-[(4-tBu-2,6-{P(O)(OiPr)₂}₂C₆H₂SnCl)₂ Pt(SnCl₃)₂] (10) and [(4-tBu-2,6-{P(O) (OiPr)₂}₂C₆H₂SnCl)₃Pt(SnCl₃)₂] (11). The compounds were characterised by elemental analyses, ¹H, ¹³C, ³¹P, ¹¹⁹Sn and ¹⁹⁵Pt NMR spectroscopy, single-crystal X-ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds 1, 3 and 4, also by Mössbauer spectroscopy. All the compounds show the tin atoms in a distorted trigonal-bipyramidal environment. The Mössbauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis-[{2,6-(Me₂NCH₂)₂C₆H₃SnCl}₂PdCl₂]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer-type ligands.

Simplicity Meets Beauty. Trapping Molecular Dimethyltin Oxide in the Novel Organotinoxo Cluster [MeN(CH2CH2O)2SnMe2·Me2SnO]3

Co-reporter:Michael Gock, Bianca Wiedemann, Christina Dietz, Chenyu Bai, Michael Lutter, Vinusuya Abeyawarathan, and Klaus Jurkschat

Organometallics 2013 Volume 32(Issue 15) pp:4262-4269

Publication Date(Web):July 12, 2013

DOI:10.1021/om400432k

The syntheses are reported of the 1,1,5-trimethyl-2,8-dioxa-5-aza-1-stannabicyclo[3.3.0]octane MeN(CH2CH2O)2SnMe2 (1), its monosodium aminoalcoholate adduct [MeN(CH2CH2O)2SnMe2·MeN(CH2CH2ONa)(CH2CH2OH)]2 (2), and the hexanuclear organotin oxo cluster [MeN(CH2CH2O)2SnMe2·Me2SnO]3 (3). The compounds were characterized by 1H, 13C, and 119Sn NMR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis. In the solid state, compound 1 is a tetramer that is brought about by intermolecular O→Sn interactions. In solution, however, it shows a monomer ⇌ dimer equilibrium that is fast on the 1H, 13C, and 119Sn NMR time scales at room temperature. All compounds show intramolecular N→Sn interactions at Sn–N distances ranging between 2.378(3) Å (2) and 3.026(3) Å (3·0.25H2O). Compound 3 can formally be regarded as a molecular dimethyltin oxide being trapped by head-to-tail complexation with a stannabicyclooctane. In solution, it slowly falls apart into 1 and Me2SnO.

Reactivity of Organotin(I) Dimers RSnSnR (R = 2,6-(Me2NCH2)2C6H3, 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2) with Diaryl Dichalcogenides, ArEEAr (E = S, Se, Te; Ar = Ph, 2-C5H4N): Control of Secondary Sn···Sn Interactions by Intramolecular Coordination and Identity of the Aryl Chalcogenate

Co-reporter:Michael Wagner, Christina Dietz, Marek Bouška, Libor Dostál, Zdeňka Padĕlková, Roman Jambor, and Klaus Jurkschat

Organometallics 2013 Volume 32(Issue 17) pp:4973-4984

Publication Date(Web):August 20, 2013

DOI:10.1021/om400694z

The reactions of the in situ prepared organotin(I) compounds RSnSnR with diaryl dichalcogenides ArEEAr provided, depending on the ratio of the reactants, the intramolecularly coordinated heteroleptic organotin(II) chalcogenoarylates RSnEAr (1, R = 2,6-(Me2NCH2)2C6H3, E = S, Ar = Ph; 2, R = 2,6-(Me2NCH2)2C6H3, E = Se, Ar = Ph; 3, R = 2,6-(Me2NCH2)2C6H3, E = Te, Ar = Ph; 6, R = 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2, E = Se, Ar = Ph; 7, R = 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2, E = Te, Ar = Ph; 8, R = 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2, E = Se, Ar = 2-C5H4N) and the corresponding organotin(IV) compounds RSn(EAr)3 (4, R = 2,6-(Me2NCH2)2C6H3, E = S, Ar = Ph; 5, R = 2,6-(Me2NCH2)2C6H3, E = Se, Ar = Ph; 10, R = 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2, E = S, Ar = 2-C5H4N), respectively. Compound 10 undergoes a thermally initiated cyclization reaction to give the benzoxaphosphastannole derivative {1(P),3(Sn)-Sn(S-Py)2-OP(O)(O-i-Pr)-6-t-Bu-4-P(O)(Oi-Pr)2}C6H2 (11). The compounds were characterized by 1H, 13C, 31P, 119Sn, and 125Te NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis. The intramolecular Sn–N and Sn–O distances range between 2.501(3) (2) and 2.815(3) Å (4) and between 2.407(2) (8·C7H8) and 2.497(2) Å, respectively. Compounds 6 and 7 show intermolecular secondary Sn···Sn interactions at distances of 3.8876(3) and 3.8379(5) Å, respectively.

[4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnL]+: An NHC-Stabilized Organotin(II) Cation and Related Derivatives

Co-reporter:Dipl.-Chem. Michael Wagner;M.Sc. Thomas Zöller;Dr. Wolf Hiller;Dr. Marc H. Prosenc;Dr. Klaus Jurkschat

Chemistry - A European Journal 2013 Volume 19( Issue 29) pp:9463-9467

Publication Date(Web):

DOI:10.1002/chem.201301477

Novel Stannatranes of the Type N(CH2CMe2O)3SnX (X = OR, SR, OC(O)R, SP(S)Ph2, Halogen). Synthesis, Molecular Structures, and Electrochemical Properties

Co-reporter:Thomas Zöller, Christina Dietz, Ljuba Iovkova-Berends, Olga Karsten, Gerrit Bradtmöller, Ann-Kristin Wiegand, Yu Wang, Viatcheslav Jouikov, and Klaus Jurkschat

Inorganic Chemistry 2012 Volume 51(Issue 2) pp:1041-1056

Publication Date(Web):December 23, 2011

DOI:10.1021/ic202179e

The syntheses of the stannatrane derivatives of the type N(CH2CMe2O)3SnX (1, X = Ot-Bu; 2, X = Oi-Pr; 3, X = 2,6-Me2C6H3O; 4, X = p-t-BuC6H4O; 5, X = p-NO2C6H4O; 6, X = p-FC6H4O; 7, X = p-PPh2C6H4O; 8, X = p-MeC6H4S; 9, X = o-NH2C6H4O; 10, X = OCPh2CH2NMe2; 11, X = Ph2P(S)S; 12, X = p-t-BuC6H4C(O)O; 13, X = Cl; 14, X = Br; 15, X = I; 16, X = p-N(CH2CMe2O)3SnOSiMe2C6H4SiMe2O) are reported. The compounds are characterized by X-ray diffraction analyses (3–8, 11–16), multinuclear NMR spectroscopy, 13C CP MAS (14) and 119Sn CP MAS NMR (13, 14) spectroscopy, mass spectrometry and osmometric molecular weight determination (13). Electrochemical measurements show that anodic oxidation of the stannatranes 4 and 8 occurs via electrochemically reversible electron transfer resulting in the corresponding cation radicals. The latter were detected by cyclic voltammetry (CV) and real-time electron paramagnetic resonance spectroscopy (EPR). DFT calculations were performed to compare the stannatranes 4, 8, and 13 with the corresponding cation radicals 4+•, 8+•, and 13+•, respectively.

Tin(II) and Tin(IV) Compounds with Scorpion-Shaped Ligands Intramolecular NSn vs. Intermolecular OSn Coordination

Co-reporter:Ljuba Iovkova-Berends;Thorsten Berends;Thomas Zöller;Gerrit Bradtmöller;Sonja Herres-Pawlis

European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 19) pp:3191-3199

Publication Date(Web):

DOI:10.1002/ejic.201200145

Abstract

The syntheses of new potentially tetradentate ligands of the type RN(CH₂CMe₂OH)₂ (1, R = Me₂NCH₂CH₂; 2, R = MeOCH₂CH₂), their tin(II) derivatives RN(CH₂CMe₂O)₂Sn (3, R = Me₂NCH₂CH₂; 4, R = MeOCH₂CH₂), the pentacarbonyltungsten complexes RN(CH₂CMe₂O)₂SnW(CO)₅ (5, R = Me₂NCH₂CH₂; 6, R = MeOCH₂CH₂) and their oxidation products with bromine, RN(CH₂CMe₂O)₂SnBr₂ (7, R = Me₂NCH₂CH₂; 8, R = MeOCH₂CH₂), are reported. The compounds were characterized by multinuclear NMR spectroscopy, elemental analysis, electrospray ionization mass spectrometry and single-crystal X-ray diffraction analysis. DFT calculations on compounds 3, 7 and 8 suggest the preference of dimeric over monomeric structures.

Intramolekular koordinierte Organozinntelluride: stabil oder labil?

Co-reporter:Marek Bou&x161;ka;Dr. Libor Dostál;Zde&x148;ka Pad&x11b;lková;Dr. Antonín Ly&x10d;ka;Dr. Sonja Herres-Pawlis;Dr. Klaus Jurkschat;Dr. Roman Jambor

Angewandte Chemie 2012 Volume 124( Issue 14) pp:3535-3540

Publication Date(Web):

DOI:10.1002/ange.201107666

Intramolecularly Coordinated Organotin Tellurides: Stable or Unstable?

Co-reporter:Marek Bou&x161;ka;Dr. Libor Dostál;Zde&x148;ka Pad&x11b;lková;Dr. Antonín Ly&x10d;ka;Dr. Sonja Herres-Pawlis;Dr. Klaus Jurkschat;Dr. Roman Jambor

Angewandte Chemie International Edition 2012 Volume 51( Issue 14) pp:3478-3482

Publication Date(Web):

DOI:10.1002/anie.201107666

Intramolecular N→Sn Coordination in Tin(II) and Tin(IV) Compounds Based on Enantiopure Ephedrine Derivatives

Co-reporter:Thomas Zöller, Ljuba Iovkova-Berends, Thorsten Berends, Christina Dietz, Gerrit Bradtmöller, and Klaus Jurkschat

Inorganic Chemistry 2011 Volume 50(Issue 17) pp:8645-8653

Publication Date(Web):July 29, 2011

DOI:10.1021/ic201203u

The syntheses and molecular structures of the intramolecularly coordinated tin(II) compounds {CH2N(Me)CH(Me)CH(Ph)O}2SnL (2, L = lone pair; 4, L = W(CO)5; 5, L = Cr(CO)5) and of the related hydroxido-substituted tin(IV) compound [{CH2N(Me)CH(Me)CH(Ph)O}2Sn(OH)]2O, 6a, are reported. Also reported are the molecular structures of the enantiopure N,N′-ethylenebis-(1R,2S)-ephedrine, {CH2N(Me)CH(Me)CH(Ph)OH}2 (1), and its hydrobromide {CH2N(Me)CH(Me)CH(Ph)OH}2·HBr (1a).

Intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)2]2C6H2Sn(X)W(CO)5 (X = Cl, F, PPh2, PPh2[W(CO)5]). Syntheses and reactivity

Co-reporter:Michael Wagner, Konstantin Dorogov, Markus Schürmann and Klaus Jurkschat

Dalton Transactions 2011 vol. 40(Issue 35) pp:8839-8848

Publication Date(Web):26 Jul 2011

DOI:10.1039/C1DT10321K

The synthesis of the intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)2]2C6H2Sn(X)W(CO)5 (1, X = Cl; 2, X = F; 3, X = PPh2) and of 4-tBu-2,6-[P(O)(OiPr)2]2C6H2Sn[W(CO)5]PPh2[W(CO)5], 4, are reported. UV-irradiation of compound 4 in tetrahydrofurane serendipitously gave the bis(organostannylene) tungsten tetracarbonyl complex cyclo-O2W[OSn(R)]2W(CO)4 (R = 4-tBu-2,6-[P(O)(OiPr)2]2C6H2), 5, that contains an unprecedented W(0)–Sn–O–W(VI) bond sequence. The compounds 1–5 were characterized by means of single crystal X-ray diffraction analysis, 1H, 13C, 19F, 31P, 119Sn NMR, and IR spectroscopy, electrospray ionization mass spectrometry (ESI–MS), and elemental analysis. Compound 4 features a hindered rotation about the Sn–P bond.

[{2,6-(Me2NCH2)2C6H3}Sn(-OH)W(CO)5]2: A Transition-Metal-Coordinated Organotin(II) Hydroxide

Co-reporter:Roman Jambor;Sonja Herres-Pawlis;Markus Schürmann

European Journal of Inorganic Chemistry 2011 Volume 2011( Issue 3) pp:344-348

Publication Date(Web):

DOI:10.1002/ejic.201000892

Abstract

The synthesis of the intramolecularly coordinated pentacarbonyltungsten–organostannylene complexes {2,6-(Me₂NCH₂)₂C₆H₃}Sn(H)W(CO)₅ (2) and [{2,6-(Me₂NCH₂)₂C₆H₃}Sn(μ-OH)W(CO)₅]₂ (3) and the solid-state molecular structure of 3, as determined by single-crystal X-ray diffraction analysis, are reported. Compound 3 is characterized by hydroxido bridges [Sn–O 2.068(5), 2.231(5) Å], an intramolecular NSn coordination bond [2.501(7) Å] and an intramolecular O–H···N hydrogen bond [O···N 2.715(8) Å].

From Pseudo-octahedral to Pseudo-trigonal Bipyramidal Configuration: Syntheses and Molecular Structures of 4-t-Bu-2,6-[(EtO)2P(O)]2C6H2BiCl2 and [1(Bi),3(P)-Bi(Cl)OP(O)(OEt)-5-t-Bu-7-P(O)(OEt)2]C6H2

Co-reporter:Katja Peveling, Markus Schürmann, Sonja Herres-Pawlis, Cristian Silvestru, and Klaus Jurkschat

Organometallics 2011 Volume 30(Issue 19) pp:5181-5187

Publication Date(Web):September 16, 2011

DOI:10.1021/om200544r

The syntheses and molecular structures in solution and in the solid state of the intramolecularly coordinated organobismuth derivatives 4-t-Bu-2,6-[(EtO)2P(O)]2C6H2BiCl2 (1) and [1(Bi),3(P)-Bi(Cl)OP(O)(OEt)-5-t-Bu-7-P(O)(OEt)2]C6H2 (2) are reported. Compound 1 crystallizes in the triclinic space group P1̅ with two pairs of crystallographically independent molecules per unit cell. Each bismuth atom shows a distorted Ψ-octahedral CCl2O2Bi configuration with the chlorine and oxygen atoms mutually trans. The intramolecular Bi···O distances range between 2.378(5) and 2.414(5) Å. The phosphabismole derivative 2 forms a head-to-tail dimer via intermolecular P═O→Bi interactions. Compound 2 crystallizes as a racemic mixture of (SP,ABi) and (RP,CBi) isomers. DFT calculations reveal the high s-character of the lone electron pairs at the bismuth atoms in compounds 1 and 2.

On the Reaction of Elemental Tin with Alcohols: A Straightforward Approach to Tin(II) and Tin(IV) Alkoxides and Related Tinoxo Clusters

Co-reporter:Thomas Zöller;Dr. Ljuba Iovkova-Berends;Christina Dietz;Dr. Thorsten Berends ;Dr. Klaus Jurkschat

Chemistry - A European Journal 2011 Volume 17( Issue 8) pp:2361-2364

Publication Date(Web):

DOI:10.1002/chem.201003338

[{2,6-(Me2NCH2)2C6H3(H2O)Sn}W(CO)5]+CB11H12: Aqua Complex of a Transition-Metal-Bound Organotin(II) Cation versus an Ammonium-Type Structure

Co-reporter:Roman Jambor;Blanka Ka&x161;ná;Stephan G. Koller;Carsten Strohmann;Markus Schürmann

European Journal of Inorganic Chemistry 2010 Volume 2010( Issue 6) pp:902-908

Publication Date(Web):

DOI:10.1002/ejic.200901087

Abstract

The molecular structures of the intramolecularly coordinated tungstenpentacarbonyl organostannylene complexes 2,6-(Me₂NCH₂)₂C₆H₃(Cl)SnW(CO)₅ and [2,6-(Me₂NCH₂)₂C₆H₃(H₂O)SnW(CO)₅]⁺(CB₁₁H₁₂)^– are reported. The latter compound is an aqua complex in which the water molecule replaces one of the two NSn coordination sites. The coordination of the water molecule is accompanied by proton transfer to the nitrogen atom. DFT calculations reveal this to be the thermodynamically most-stable structure.

The First Examples of a Crown Ether Intramolecularly Encapsulating Mono- and Diorganotin Dications: Synthesis and Structures of [PhSnCH2([16]crown-5)][ClO4]2 and [HOSnCH2([16]crown-5)][Y]2 (Y=ClO4, CF3SO3)

Co-reporter:AlainCharly TagneKuate Dr.;Markus Schürmann Dr.;Dieter Schollmeyer Dr.;Wolf Hiller Dr. Dr.

Chemistry - A European Journal 2010 Volume 16( Issue 27) pp:8140-8146

Publication Date(Web):

DOI:10.1002/chem.200903572

Abstract

The reaction of silver perchlorate with [PhI₂SnCH₂([16]crown-5)] (1) and [I₃SnCH₂([16]crown-5)] (2) gave the organotin(IV)-substituted crown ether complexes [PhSnCH₂([16]crown-5)][ClO₄]₂ (3) and [HOSnCH₂([16]crown-5)][Y]₂ (4: Y=ClO₄, 5: Y=CF₃SO₃), respectively. All compounds have been isolated as air-stable materials and characterised by ¹H, ¹³C, ¹¹⁹Sn and ¹¹⁹Sn MAS (5) NMR spectroscopy, ESIMS spectrometry, elemental analysis and by single-crystal X-ray diffraction analysis. The molecular structures of 3–5 show that the tin(IV) cation fits perfectly into the crown ether cavity and is coordinated by the five oxygen atoms of the ring to give a pentagonal bipyramidal configuration about the central metal cation. Notably, compounds 4 and 5 contain the first monomeric monoorganotin dication. Moreover, there are ³J(¹H,¹¹⁹Sn) coupling constants to the CH₂CH proton of 377 (3) and 470 Hz (4, 5) that are, to the best of our knowledge, the biggest such couplings ever reported.