At the limits of bisphosphonio‐substituted stannylenes

Nasemann, Sina; Franz, Roman; Kargin, Denis; Bruhn, Clemens; Kelemen, Zsolt; Gutmann, Torsten; Pietschnig, Rudolf

doi:10.1002/asia.202300950

Chemistry An Asian Journal

2023

DOI: 10.1002/asia.202300950

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At the limits of bisphosphonio‐substituted stannylenes

Sina Nasemann,

Roman Franz,

Denis Kargin

et al.

Abstract: Donor stabilization of Sn(II) and Pb(II) halides with 1,1’‐ferrocenylene bridged bisphosphanes has been explored for Fe(C5H4P(C6H5)2)2 (dppf), and Fe(C5H4PH(C4H9))2. These bisphosphanes are reacted with SnBr2 and PbCl2 with and without additional Lewis acid (AlCl3) forming acyclic and cyclic donor adducts from which the latter represent bisphosphoniotetrylenes. Since dynamic exchange in solution is observed, characterization includes solution and solid‐state NMR in addition to SC‐XRD, amended by DFT calculatio… Show more

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Cited by 4 publications

References 40 publications

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Intramolecularly O,N,O‐Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation

Alnasr,

Mroß,

Platzek

et al. 2024

Chemistry A European J

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We report the syntheses of tin(II) salts of the types [L1SnX]SnX3 [L1 = 2,6‐{(i‐PrO)2(O)P}2C5H3N: 1, X = Cl; 2, X = Br], [L2SnCl]SnCl3 [L2 = 2‐{(i‐PrO)Ph(O)P}‐6‐{(i‐PrO)2(O)P}C5H3N: 3], [L3SnX]SnX3 [L3 = 2,6‐{MeO(O)C}2C5H3N: 4, X = Cl; 5, X = Br], [L4SnX]SnX3[L4 = 2,6‐{Et2N(O)C}2C5H3N: 6, X = Cl; 7, X = Br]. These compounds were obtained by addition of SnX2 to the corresponding ligand inducing autoionization of the respective tin(II) halide. The thermal stability of 1, 3, and 4 was elucidated, giving, under ester cleavage and cyclisation, the tin(II) derivatives 8‐12. The reaction of [L1SnCl]SnCl3 (1) with W(CO)4(thf)2 afforded the tungsten tetracarbonyl complex [{L1SnCl}{SnCl3}W(CO)4] (13), representing the first example in which a tin(II) stannate anion and a tin(II) stannylium cation simultaneously coordinate to a transition metal centre. The compounds were characterized by single crystal X‐ray diffraction analyses and in part by elemental analyses, IR and NMR spectroscopy, electrospray ionization mass spectrometry. DFT calculations accompany the experimental work.

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Intramolecularly O,N,O‐Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation

Alnasr,

Mroß,

Platzek

et al. 2024

Chemistry A European J

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Unraveling the Stereoisomer Configurations of 1,1’‐bis(tert‐butylphosphino)Ferrocene in the Gas Phase

Sun,

Kargin,

Kelemen

et al. 2024

ChemPhysChem

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The molecular structure of a ferrocene derivative with adjacent centers of chirality, 1,1’‐bis(tert ‐ butylphosphino)ferrocene, has been examined in the gas phase using broadband microwave spectroscopy under the isolated and cold conditions of a supersonic jet. The diastereomers of 1,1’‐bis(tert‐butylphosphino)ferrocene can adopt homo‐ and hetero‐chiral configurations, owing to the P‐chiral substituents on the cyclopentadienyl rings. Moreover, the internal ring rotation of each diastereomer gives rise to four conformers with eclipsed ring arrangements, where the two tert‐butylphosphino groups were separated by dihedral angles of approximately 72◦, 144◦, 216◦, and 288◦ with respect to the two ring centers. The interconversion barriers between the conformations are below 2 kJ/mol, whereas the pyramidal inversion of the tert‐butylphosphino groups is hindered by more than 140 kJ/mol, calculated at the B3LYP‐D3(BJ)/def2‐QZVP level of theory. In the experimental microwave spectrum, we unambiguously identified the two global‐minimum diastereomers with 72◦ conformations. The absence of other conformers can be attributed to the relaxation dynamics in the supersonic jet, which transfers the high‐energy conformers to the respective global‐minimum geometries. Additionally, we discovered that London dispersion inter‐ actions between the two tert‐butylphosphino groups play a crucial role in stabilizing the structures of this ferrocene complex.

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Synthesis and Characterization of NHC Stabilized Bis(phenylsulfanyl)stannylene

Mammadova,

Bruhn,

Pietschnig

2024

Zeitschrift anorg allge chemie

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Reaction of two equivalents of ((CH3)3Si)2C(C6H5)SLi·3THF with SnCl2·IPr (IPr=:C[N(Diip)C(H)]2, Diip= 2,6 i‐(CH3)2CH(C6H5) led to fragmentation of the organolithium component and gave IPr·Sn(SPh)2, compound 3. The latter compound has been further prepared from Ph‐SSi(CH3)3 whereas disproportionation of the Sn(II) species was observed when starting from Ph‐SLi. Stannylene adduct 3 has been characterized spectroscopically and its structure was explored with single crystal X‐ray diffraction (SCXRD). The carbene donor in 3 can be displaced by chloride upon formal HCl addition giving rise to the ionic stannylene adduct 3a IPr+[SnCl(SPh)2]‐, the structure of which was investigated with SCXRD as well.

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At the limits of bisphosphonio‐substituted stannylenes

Cited by 4 publications

References 40 publications

Intramolecularly O,N,O‐Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation

Intramolecularly O,N,O‐Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation

Unraveling the Stereoisomer Configurations of 1,1’‐bis(tert‐butylphosphino)Ferrocene in the Gas Phase

Synthesis and Characterization of NHC Stabilized Bis(phenylsulfanyl)stannylene

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