Inter- vs. intramolecular carbon-hydrogen activation: a carbon-hydrogen-iridium bridge in [IrH2(mq)L2]BF4 and a CH + M .fwdarw. CMH reaction trajectory

Homogeneous Hydrogenation of Tri‐ and Tetrasubstituted Olefins: Comparison of Iridium‐Phospinooxazoline [Ir‐PHOX] Complexes and Crabtree Catalysts with Hexafluorophosphate (PF6) and Tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate (BArF) as Counterions

“…[7] Attempts to obtain complex 13 directly from commercially available Crabtree catalyst by anion exchange were unsuccessful. Therefore, the route used by Crabtree [8] for the synthesis of the corresponding hexafluorophosphate 1 was chosen (Scheme 2). By a modified procedure, starting from [IrA C H T U N G T R E N N U N G (COD)Cl] 2 , pyridine and NaBAr F , the bisA C H T U N G T R E N N U N G (pyridine) complex 12 was readily obtained.…”

A Capped Octahedral MHC6 Compound of a Platinum Group Metal

“…[14] In accordance with these values, the agostic interactions persist in [D 2 ]dichloromethane at temperatures lower than 223 K. Thus,t he 1 HNMR spectra at these temperatures contain two phenylr esonances at 1.86 and 1.49 ppm, whereas the INEPT 13 Cs pectrum at 213 Ks hows CÀHc oupling constantso f1 14 and 112Hzf or phenylr esonances at 98.4 and 92.9 ppm, respectively,w hich are about 50 Hz lower than the other 1 J CÀH coupling constants. This extreme case [15] of two agostici nteractions is forced by the exceptionally high Lewis acidity of the generated 14-valence-electron, non p-stabilized, osmium(II) cation.…”

Structure of [Pt(C6H5)2(btz-N,N')].CHCl3, btz = 2,2'-bi-5,6-dihydro-4H-1,3-thiazine

“…The carbon to platinum separation is 3.44 A. The Pt--.H separation (for the H atom in calculated position) of 2.48 A is in the range found for weak intramolecular M.--H interactions (Crabtree, Holt, Lavin & Morehouse, 1985).…”