The reaction of the group-13 alkyls ER3 (E=Al, Ga, In; R=CH2t-Bu, CH2 SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)]

Well‐Defined Heterobimetallic Reactivity at Unsupported Ruthenium–Indium Bonds

“…Similarc ontacts have been noted in both [Pt(dcpe)(InR 2 )(R)] (dcpe = Cy 2 P(CH 2 ) 2 PCy 2 ,R = CH 2 tBu) [22] and [Ir(PMe 3 ) 3 (InEt 2 )(Et)H], [11f] which are the only crystallographically characterised precedents that feature adjacent alkyl and indyl ligands. Severalc omputed structures show either ab ridging Me (I(1-4)1)o rs hort, non-bonded In···Me contacts( I(1-4)2, 4 and 6).…”

“…4 also readily adds CO to give 6 at À14.0 kcal mol À1 .M etransfer onto the neighbouringI nMel igand then proceeds with ab arrier of 10.4 kcal mol À1 to form the indyl intermediate I(6-7) (G = À14.1 kcal mol À1 ). [22] All computed RuÀIn distances are below 2.88 ,t he sum of the covalent radii defined by Alvarez and co-workers. [21] The computed geometries in Figures 2a nd 3s how ar ange of RuÀIn distances, from 2.45 for species 4 to 2.84 in I(6-7).F or 5 and 7 the calculations slightly overestimate the RuÀIn distances, at rend seen in relateds tudies on dialkylgallyla dducts.…”

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

“…There is precedent for this intramolecular coordination mode: Fischer and co-workers have reported the gallium adduct 40 . 83 Related hydrogenation reactions of platinium diene complexes either bearing a Z-type Al ligand or in the presence of Ga I co-ligands lead to the formation of heterobimetallic complexes bearing terminal hydride ligands on the transition metal (Fig. S1, ESI † ).…”

Structure and bonding analysis of dimethylgallyl complexes of cobalt, rhodium and iridium [Me(PMe3)2(Me3GaCl)M(GaMe2)] (M = Co, Rh, Ir) and [Me(PMe3)2ClIr(GaMe2)]: A theoretical study

“…Synthesis, structure and spectroscopic studies of dialkylgallyl complex of iron [(h 5 -C 5 Me 5 )(CO) 2 FeGa( t Bu) 2 ] were reported by Power and coworkers [22]. Structure and bonding analysis in model complex of dialkylgallyl platinum complex [(dcpe)Pt{Ga(CH 2 SiMe 3 ) 2 }(CH 2 SiMe 3 )] has been investigated [23]. Recently, a structurally characterized dimethylgallyl iridium complex [(Me)Ir(Me3GaCl)(GaMe 2 )(PCy 3 ) 2 ] has been reported by Merino and coworkers [24].…”