Synthesis and reactivity of dinuclear µ-silyl complexes of ruthenium having three-centre two-electron Ru–H–Si interactions

MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si - Ru, Si - Rh and Si - Pd BONDS

“…While the Ru 0) -Si distances lie in the reported range, the Ru< 2 ) -Si (2) distance is much longer. The elongation of agostic Ru -Si bonds (average 2.56 A) was also observed for symmetric complex 32 (R=R'=R"=Et) [43], Compound 33 [44] has two long Ru (l) -Si (]) (2.497 A) and Ru< 2) -Si (2) (2.517 Ä) bonds and two short ones (2.439 and 2.435 A), however, the difference is much smaller than that observed in complexes 32.…”

“…The Ru -Si bond distances for these two derivatives (2. 43 Oxidative addition of bis(trimethylsilyl)acetylene to Ru(H) 2 (CO)('Bu 2 MeP) 2 proceeds with Si -C bond cleavage and addition of both Si and C atoms to the ruthenium center. The crystal structure of this product 10 indicates that the ruthenium atom has a square-pyramidal coordination with trans phosphine ligands.…”

“…The Ru -Si distance of 2.384 A is shorter than the Ru -Si bonds including Ru-H-Si interactions in the silyl complexes 30 and 32. 30 31 The Ru 2 Si2 core of bis^-silyl) complexes 32 [42,43] forms a folded quadrangle. Different Ru -Si bond lengths in compound 32 (R='Bu, R'=H, R"=Ph) represent the existence of two-electron three-center interactions around Ru (2 ).…”

Towards Reagents for Bimetallic Activation Reactions: Polyhydride Complexes with Ru2H3, Ru2ZnH6, and Cu2Ru2H6 Cores

“…[2c,3] Quantum chemical calculations show that the metal atoms can act in a truly synergistic manner in such reactions. [2] Oligonuclear hydridoruthenium complexes based on other ligand [Cu 2 {Ru(μ-H) 3 (PPh 3 ) 3 } 2 ] (4) were synthesized and characterized by multinuclear NMR and IR spectroscopy, and microanalysis. Current investigations are limited to a small family of compounds that typically contain pentamethylcyclopentadienyl (Cp*) ligands.…”

“…[5] The fac-[RuH 3 (PR 3 ) 3 ]anion (A) should be an attractive synthon for new homo-and heteronuclear polyhydride structures, but few complexes of this building block have been described. The compound [K( [18]crown-6){Ru(μ-H) 3 (PTol 3 ) 3 }] is accessible in good yield from [RuHCl(PPh 3 ) 3 ] and KBH(sBu) 3 . The compound [K( [18]crown-6){Ru(μ-H) 3 (PTol 3 ) 3 }] is accessible in good yield from [RuHCl(PPh 3 ) 3 ] and KBH(sBu) 3 .…”