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

Abstract

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.