Ruthenium and Osmium Germyl Complexes Derived from the Reactions of MXCl(PPh₃)₃ (M = Ru, Os; X = Cl, H) with Terphenylchlorogermylene (C₆H₃‐2,6‐Trip₂)GeCl (Trip = 2,4,6‐iPr₃C₆H₂)

Abstract

The reactions of MXCl(PPh 3 ) 3 (M = Ru, Os; X = Cl,

Synthesis, Structure, and Bonding of Group 8 Transition Metal Germyl Complexes, [Cp*M{κ2-Ge,S-GeCl2C7H4NS2}(PPh3)] (M = Ru or Os)

“…Therefore, complex 2b can be described as [Cp*Os­{κ 2 - Ge , S -GeCl 2 C 7 H 4 NS 2 }­(PPh 3 )]. The Os–Ge bond distance of 2.364 Å is shorter than those of tethered germyl complex IIIB (2.406 Å) and terminal germyl complexes of osmium (2.421–2.575 Å) . The overall bonding parameters of the osmacycle (Os–Ge–N–C–S) in 2b also suggest a tethered germyl complex of osmium.…”

“…Among them, the TM complexes with a tethered tetryl ligand are interesting owing to their structural aspects. − ,− For example, the Wright group reported a tethered silyl complex [(CO)­Ru­(κ 2 -( Si , N )-SiPh 2 NHC 5 H 4 N)­(κ 2 -S 2 CNMe 2 )­(PPh 3 )] ( I ), which shows a bonding situation that is intermediate between “tethered silyl” (predominant) and ‘base-stabilized silylene” within the five-membered {Ru–N–C–N–Si} ring (Chart ). They have also isolated a tethered stannyl complex [Os­(Me)­{κ 2 -( Sn , O )-SnMe 2 OC (Me)­O}­(CO)­(PPh 3 ) 2 ] ( II ) from a methyl migration between osmium and tin atoms of an osmium trimethylstannyl complex [Os­(SnMe 3 )­Cl­(CO)­(PPh 3 ) 2 ] .…”

“…The structural parameters of complex II suggest a base-stabilized stannylene character. Wen and co-workers have isolated the ruthenium and osmium tethered dichlorogermyl complexes Cl­(PPh 3 ) MGeCl 2 (C 6 H 3 -2-{η 6 -Trip}-6-Trip) (Trip = 2,4,6- i Pr 3 C 6 H 2 ) ( IIIa : M = Ru, and IIIb : M = Os) from the insertion of the monochlorogermylene ligand [(C 6 H 3 -2,6-Trip 2 ) GeCl] into the M–Cl bond of [MClX­(PPh 3 ) 3 ] (M = Ru, Os; X = Cl, H) . Boyd and co-workers reported a tethered germyl ruthenium complex [Ru­(κ 2 -(S 2 CNMe 2 )­(CO))­(κ 2 -( Ge , S )-Ge­[ p -tolyl] 2 S 2 CNMe 2 )­(PPh 3 )] ( IV ) by substituting one of the p -tolyl groups attached to the germanium of the coordinatively unsaturated ruthenium germyl complex [Ru­(CO)­(Ge­[ p -tolyl] 3 )­Cl­(PPh 3 ) 2 ] .…”