Abstract
A hydrido platinum(II) complex with a dihydrosilyl ligand, [cis-PtH(SiH2Trip)(PPh3)2] (2) was prepared by oxidative addition of an overcrowded primary silane, TripSiH3 (1, Trip = 9-triptycyl) with [Pt(η2-C2H4)(PPh3)2] in toluene. The ligand-exchange reactions of complex 2 with free phosphine ligands resulted in the formation of a series of (hydrido)(dihydrosilyl) complexes (3–5). Thus, the replacement of two PPh3 ligands in 2 with a bidentate bis(phosphine) ligand such as DPPF [1,2-bis(diphenylphosphino)ferrocene] or DCPE [1,2-bis(dicyclohexylphosphino)ethane] gave the corresponding complexes [PtH(SiH2Trip)(L-L)] (3: L-L = dppf, 4: L-L = dcpe). In contrast, the ligand-exchange reaction of 2 with an excess amount of PMe3 in toluene quantitatively produced [PtH(SiH2Trip)(PMe3)(PPh3)] (5), where the PMe3 ligand is adopting trans to the hydrido ligand. The structures of complexes 2–5 were fully determined on the basis of their NMR and IR spectra, and elemental analyses. Moreover, the low-temperature X-ray crystallography of 2, 3, and 5 revealed that the platinum center has a distorted square planar environment, which is probably due to the steric requirement of the cis-coordinated phosphine ligands and the bulky 9-triptycyl group on the silicon atom.
Highlights
The transition metal catalyzed synthesis of functionalized organosilicon compounds gained substantial momentum during the past few decades [1]
The low-temperature X-ray crystallography of 2, 3, and 5 revealed that the platinum center has a distorted square planar environment, which is probably due to the steric requirement of the cis-coordinated phosphine ligands and the bulky 9-triptycyl group on the silicon atom
The oxidative addition of hydrosilanes with platinum(0) complexes is an efficient method for the generation of the platinum(II) hydride species, which has been proposed as a key intermediate in platinum-catalyzed hydrosilylations [2,3,4,5,6] and bis-silylations [7,8], as well as the dehydrogenative couplings of hydrosilanes [9,10,11,12,13]
Summary
The transition metal catalyzed synthesis of functionalized organosilicon compounds gained substantial momentum during the past few decades [1] Among these catalytic conversions, the oxidative addition of hydrosilanes with platinum(0) complexes is an efficient method for the generation of the platinum(II) hydride species, which has been proposed as a key intermediate in platinum-catalyzed hydrosilylations [2,3,4,5,6] and bis-silylations [7,8], as well as the dehydrogenative couplings of hydrosilanes [9,10,11,12,13]. In 2000, Tessier et al reported that the reaction of a primary silane with a bulky m-terphenyl group with [Pt(PPr)3 ] produced the first example of a stable hydrido(dihydrosilyl) complex [cis-PtH(SiH2 Ar)(PPr3 )2 ] (Ar = 2,6-MesC6 H3 ) [35]. Complexes, here and the characterization synthesis and of a series of mononuclear (hydrido)(dihydrosilyl) complexes [PtH(SiH
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