O. Prakash, Pradhumn Singh, G. Mukherjee
Apr 3, 2012
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Journal
Organometallics
Abstract
The in situ generated ArE¯ (E = S or Se) reacts with (2-chloromethyl)pyridine in N2 atmosphere, resulting in half-pincer (N, S/Se) ligands (2-arylchalcogenomethyl)pyridine (L1–L3; aryl = Ph/2-pyridyl for S, Ph for Se). Half-sandwich complexes [(η5-Cp*)Rh(L)Cl][PF6] (1, 2), [(η5-Cp*)Rh(L2)CH3CN][PF6]2 (3), and [(η5-Cp*)Ir(L)Cl][PF6] (4–6), where L = L1–L3, have been synthesized by reacting L with [(η5-Cp*)RhCl(μ-Cl)]2 and [(η5-Cp*)IrCl(μ-Cl)]2 respectively. The ligands and complexes have been characterized by IR, HR-MS, and 1H, 13C{1H}, and 77Se{1H} NMR spectra. The single-crystal structures of all the complexes (1–6) have been determined with X-ray crystallography [Rh–S, Rh–Se, Ir–S, Ir–Se bond distances: 2.383(2)/2.353(2), 2.4867(9), 2.343(2)/2.341(3), 2.453(1) A, respectively]. Each metal has pseudo-octahedral half-sandwich “piano-stool” geometry. The PF6– ions in crystals are packed between half-sandwich complex molecules, resulting in various H···F secondary interactions. Complexes 1–6 have been explo...