Zur synthese und struktur von pentacarbonylmetall(0)-Komplexen intramolekular basenstabilisierter zinn(III)-verbindungen

doi:10.1016/S0022-328X(00)99731-6

Journal of Organometallic Chemistry

Volume 308, Issue 3, 15 July 1986, Pages 325-334

https://doi.org/10.1016/S0022-328X(00)99731-6 Get rights and content

Abstract

The synthesis and structure of pentacarbonylmetal(0) complexes of the types (C0)₅MSn(XCH₂CH₂)₂E (M = Cr, Mo, W; X = O, S; E = NR, PPh, O, S) and (CO)₅ WSn(SCH₂CH₂)₂E · py (E = NMe, O, S) are reported.

¹¹⁹Sn and ¹³C NMR studies show the compounds with X = O and E = NR to be dimeric whereas the derivatives with X = S have been found to be monomeric. The π-acceptor behaviour of the ligands Sn(XCH₂CH₂)₂E is comparable to that of the phosphanes. The barriers to internal rotations about the nitrogencarbon bonds have been determined for the NBu^t derivatives.

Zusammenfassung

Es wird über die Synthese und Struktur von Pentacarbonylmetall(0)-Komplexen der Typen (CO)₅MSn(XCH₂CH₂)₂E (M = Cr, Mo, W; X = O, S; E = NR, PPh, O, S) und (CO)₅WSn(SCH₂CH₂)₂E · Py (E = NMe, O, S) berichtet. ¹¹⁹Sn- und ¹³C-NMR-Untersuchungen zeigen, dass die Verbindungen mit X = O und E = NR als Dimere vorliegen, während die Derivative mit X = S monomer gebault sind. Das π-Akzeptorverhalten der Liganden Sn(XCH₂CH₂)₂E ist dem der Phosphane vergleichbar. Für die NBu^t-Derivative werden die Rotationsbarrieren um die Stickstoff-Kohlenstoff-Bindung bestimmt.

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Structural diversity of organotin(IV) complexes self-assembled from hydroxamic acid and mono- or dialkyltin salts
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The 119Sn NMR spectroscopy data of compound 3–6 (δ = −380 ppm for 3; −377 ppm for 4; −367 ppm for 5; −353 ppm for 6) show signals in the normal range for six-coordinate mono-n-butyltin(IV) derivatives, which are similar to that found in the compounds reported previously [25,26]. For compounds 7 and 8, the 119Sn NMR spectroscopic data show one resonance signal at δ = −482 ppm for 7 and −480 ppm for 8, respectively, which fall in the range corresponding to a type of seven-coordinated tin compounds [27]. Selected bond lengths and angles of complexes 1 and 2 are listed in Table 1.
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With heavier TM e.g. in the triad Cr, Mo to W, π-back donation increases because of the relativistic destabilisation of the d-orbitals, which means, that they get closer to the high energy LUMOs of the low valent tetrele [18].1 The situation is quite different for N-heterocyclic carbene (NHC) ligands, where π-back donation is considerably reduced [20]. In the X2E–TM(Cl) series (X2E = NHC, R2Si, R2Ge; TM = Cu, Ag, Au), the TM–E bonds show a high degree of coulombian interaction with covalent contributions from σ-donation, but weak π-back donation.
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Les longueurs de liaison Sn–TM suivent un profil parabolique sur une période de TM, selon R, B et L_n. Les modifications observées sur R₂Sn-M(CO)_n classent R₂Sn comme faible accepteur π, raccourcissement de Sn-R et ouvertures d'angles R–Sn–R correspondant à une augmentation du caractère s de la liaison Sn-TM. Un rayon de coordination r_coord(SnR₂) de 1.18 Å est proposé.
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Organotin and related tin containing compounds are a recurring motif in organometallic chemistry. Here we report a new complex resulting from the reaction of tin (II) chloride with a dithioether diallyl ether ligand created as a side product from other research in our lab. This new complex is reasonably stable and can be synthesized on the bench top with no extraordinary measures required to exclude air or moisture. Its crystal structure reveals a five coordinate pseudo-square pyramidal geometry around tin, with the ligand binding the metal through its thioether sulfurs and the chlorides bridging.
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Zur synthese und struktur von pentacarbonylmetall(0)-Komplexen intramolekular basenstabilisierter zinn(III)-verbindungen

Abstract

Zusammenfassung

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

J. Organomet. Chem.

J. Magn. Res.

J. Organomet. Chem.

J. Cryst. Spec. Res.

Z. Anorg. Allg. Chem.

Usp. Chim.