E‑Selective Synthesis and Coordination Chemistry of Pyridine-Phosphaalkenes: Five Ligands Produce Four Distinct Types of Ru(II) Complexes

Pyridine-phosphaalkene (PN) ligands 2a–e were prepared in an E-selective fashion using phospha-Wittig methodology. Treatment of these five ligands, varying only in their 6-substituent with RuCl₂(PPh₃)₃, produced four distinct types of coordination complexes: pyridine-phosphaalkene-derived 3b,d, cyclized 4e, and six-coordinate 5a and 6c. Prolonged heating of 3b,d in THF resulted in C–H activation of the Mes* group and cyclization to give 4b,d featuring a bidentate pyridine-phospholane ligand bound to the metal center. Complex 5a, also possessing a newly formed phospholane ring, contained a different spatial arrangement of donors to Ru­(II) with an agostic Ru–H–C interaction serving as the sixth donor to the transition metal center. Ligands 2b,d,e and Ru­(II) complexes 3b, 4b,e and 5a were all characterized by X-ray crystallography. Six-coordinate 6c featured a structure similar to 4b,d,e, but with the CF₃ substituent acting as a weakly bound sixth ligand to the Ru­(II) center, as observed by ³¹P­{¹H} and ¹⁹F NMR spectroscopy. The calculated structure of 6c established that the closest Ru- - -F contact was at 2.978 Å.