Synthesis and characterization of novel intramolecularly O,C,O-coordinated heteroleptic organostannylenes and their tungstenpentacarbonyl complexes

Bis‐Sulfonyl O,C,O‐Chelated Metallylenes (Ge, Sn) as Adjustable Ligands for Iron and Tungsten Complexes

“…The Sn−O bond lengths (2.381(3) and 2.416(3) Å) are between those reported for [SnW(CO) 5 Cl{2,6‐[P(O)(O i Pr) 2 ] 2 ‐4‐ t Bu‐C 6 H 2 }] (2.313(2) and 2.346(2) Å) and for [SnW(CO) 5 Cl[{2,6‐(ROCH 2 ) 2 C 6 H 3 }] (R=Me, 2.391(5) and 2.389(5) Å; R= t Bu, 2.464(3) and 2.513(3) Å) . The Sn−W distance (2.718(1) Å) is slightly shorter than the corresponding distances in related complexes containing pincer ligand with phosphonato groups (2.7263(11) Å) or amino, alkoxy groups (2.7630(3), 2.7321(5), and 2.7655(4) Å, respectively). No noticeable variations of the Ge−O bond lengths were observed between the two germylene–iron 4 and tungsten 6 complexes, but they are shorter than those in the germylene 2 .…”

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

“…[15] The 119 Sn NMR spectrum of 2 displayed a sharp resonance at δ = 199 ppm with a 1 J( 119 Sn-183 W) constant of 870 Hz. This value is smaller than the corresponding couplings in the chlorido-substituted derivative 1 (1186 Hz) and in the oxygen-coordinated complexes [2,6-(ROCH 2 ) 2 C 6 H 3 Sn(X)-W(CO) 5 ] [R = Me, X = Cl (1245 Hz); R = tBu, X = Cl (1289 Hz); R = Me, X = H (1242 Hz)] [15] and [4-tBu-2,6-{(O-iPr) 2 P(O)} 2 C 6 H 2 ]Sn(Cl)W(CO) 5 (1366 Hz). [14] No single crystals of compound 2 suitable for X-ray diffraction analysis could be obtained, and consequently the structure of 2 in the solid state remains unknown.…”

The Role of Monoanionic Aryl Pincer Ligands in the Stabilization of Group 14 Metallylenes

“…[33] Using an O,C,O-type pincer ligand, where the ortho substituents on the aromatic ring are Odonor ether groups, stannylenes 31 and 32 were synthesized, as illustrated in Scheme 8. [57,59] Both stannylenes were characterized by NMR spectroscopy and mass spectrometry, exhibiting the characteristics for a pincer stabilized chlorostannylene. [57] By adding W(CO)5SnCl2 to [2,6-(ROCH2)2C6H3]Li (R = Me, t-Bu), stannylene pentacarbonyl-tungsten complexes 84 and 85 were obtained, as presented in Scheme 13.…”

“…[57,59] Both stannylenes were characterized by NMR spectroscopy and mass spectrometry, exhibiting the characteristics for a pincer stabilized chlorostannylene. [57] By adding W(CO)5SnCl2 to [2,6-(ROCH2)2C6H3]Li (R = Me, t-Bu), stannylene pentacarbonyl-tungsten complexes 84 and 85 were obtained, as presented in Scheme 13. [57] Scheme 13.…”

“…[57] By adding W(CO)5SnCl2 to [2,6-(ROCH2)2C6H3]Li (R = Me, t-Bu), stannylene pentacarbonyl-tungsten complexes 84 and 85 were obtained, as presented in Scheme 13. [57] Scheme 13. Synthesis of O,C,O-pincer stabilized stannylene and stannylene-tungsten complex stannylene-chromium complex…”